CN1143332C - Process for producing rare earth bond magnet, composition for rare earth bond magnet, and rare earth bond magnet - Google Patents

Process for producing rare earth bond magnet, composition for rare earth bond magnet, and rare earth bond magnet Download PDF

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Publication number
CN1143332C
CN1143332C CNB971905533A CN97190553A CN1143332C CN 1143332 C CN1143332 C CN 1143332C CN B971905533 A CNB971905533 A CN B971905533A CN 97190553 A CN97190553 A CN 97190553A CN 1143332 C CN1143332 C CN 1143332C
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China
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rare
temperature
magnet
mentioned
binder resin
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CN1194717A (en
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井熊健
篠原孝友
塩原清
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Seiko Epson Corp
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Seiko Epson Corp
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Priority claimed from JP8061495A external-priority patent/JPH09260170A/en
Priority claimed from JP07764296A external-priority patent/JP3653852B2/en
Priority claimed from JP16127496A external-priority patent/JP3658868B2/en
Application filed by Seiko Epson Corp filed Critical Seiko Epson Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0558—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together bonded together
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0578—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together bonded together
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0579—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B with exchange spin coupling between hard and soft nanophases, e.g. nanocomposite spring magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • Y10S977/775—Nanosized powder or flake, e.g. nanosized catalyst
    • Y10S977/777—Metallic powder or flake

Abstract

A process for producing a rare earth bond magnet comprising the steps of first mixing rare earth magnetic powder, a binding resin and an anti-oxidant at a predetermined ratio, kneading the mixture at a temperature higher than a thermal deformation temperature of the binding resin, granulating or classifying the kneadate to a mean particle diameter of, e.g., about 0.01 to 2 mm, press-molding the resulting granular material at a first temperature at which the binding resin is softened or molten, and cooling the resulting molded article under a pressure to a second temperature lower than at least the first temperature. Consequently, a rare earth bond magnet having a low porosity, high dimensional accuracy and excellent magnetic characteristics can be obtained.

Description

The manufacture method of rare-earth adhesive magnet and rare-earth adhesive magnet
Technical field
The invention relates to the method for the bonding manufacturing of the ferromagnetic powder rare-earth adhesive magnet that utilizes adhesive will contain rare earth element, used rare-earth adhesive group of magnets compound in rare-earth adhesive magnet is made, and rare-earth adhesive magnet.
Background technology
Bonded magnet is that mixture (compound) processing and manufacturing with ferromagnetic powder and binder resin (organic bond) becomes desirable magnet shape, in this bonded magnet, by the magnet that magnetic material constituted that the ferromagnetic powder of rear earth containing element is formed, be called rare-earth adhesive magnet.Manufacturing about this rare-earth adhesive magnet, for example in following document, have disclosed, that is, special public clear 53-34640 communique, special public clear 46-31841 communique, special fair 04-74421 communique, spy open clear 59-136907 communique, spy and open clear 59-213104 communique, spy and open flat 02-153509 communique, spy and open clear 60-211908 communique, spy and open clear 60-216523 communique, spy and open that clear 61-164215 communique, spy are opened clear 59-103309 communique, the spy opens flat 03-108301 communique etc.
As the manufacturing process of rare-earth adhesive magnet, rough classification has compression forming method, injection molding method and extruding formation method.
Compression forming method is that said mixture is filled in the extrusion die, at room temperature carries out compression molding and obtains formed body, and subsequently, be under the situation of thermosetting resin at binder resin, make its sclerosis form the method for magnet.This method is compared with other method because the binder resin amount both made seldom also and can be shaped, the amount of resin in the gained magnet seldom, so help improving magnetic characteristic.
Extruding formation method, be said mixture with heating and melting from the mould of extrusion moulding machine, extrude on the limit, the limit cooling curing cuts into desirable length, makes the method for magnet.This method, shape for magnet, the degree of freedom is bigger, thus its advantage can produce at an easy rate very thin, the magnet of long size, but when guaranteeing to be shaped the flowability of fused mass, so need be than the more binder resin of compression forming method, therefore, the amount of resin in the gained magnet is a lot, and its shortcoming is that the magnetic characteristic trend reduces.
Injection molding method is with the said mixture heating and melting, is keeping under the abundant mobile state this fused mass being injected in the mould method of formation definite shape magnet.This method is also bigger than extruding formation method with respect to the degree of freedom of magnet shape.Its advantage is to produce difform magnet especially easily.Yet, the flowability of fused mass during shaping, owing to require to be higher than above-mentioned extruding formation method, so require the addition of binder resin more than above-mentioned extruding formation method, therefore, in the magnet that obtains, amount of resin is a lot, its shortcoming is that magnetic characteristic is tending towards reducing.
More than in each method, compression forming method is compared with other method, can be processed into the very high magnet of magnetic property.But when utilizing compression molding manufactured bonded magnet in the past, there is following shortcoming.
The 1st, because the porosity of rare-earth adhesive magnet formed body demonstrates the trend that increases, so the mechanical strength of magnet is very weak, corrosion resistance is very poor.Therefore, particularly in the compression forming method, forming pressure must 70kgf/mm 2More than, utilizing high-pressure forming, the bag that the back that is shaped is used its enforcement anticorrosion is coated with processing, etc.Yet, the high-pressure forming method, the burden that mould and forming machine bear is very big, so require it to maximize, causes the raising of manufacturing expense.And, being coated with when handling with bag carrying out anticorrosion, consequent corrosion resistance can not be fully improved.
The 2nd, mixture, though can former state directly or block in shaping, thus, particularly in the compression forming method, be difficult to mixture is filled in the mould, and mixture can not be filled in each corner of mould.The mixture of consolidated block, the loading in mould also can not be adjusted meticulously.
The 3rd, use when containing the compression molding of thermosetting resin mixture, as thermosetting resin, can use solid, shaped under the room temperature or liquid, any situation forming temperature all is a room temperature.Therefore, when using the former hard resin, formability is very poor, when using thermoplastic resin, demonstrates taking advantage of a favourable situation that porosity increases, simultaneously, resin and ferromagnetic powder dispersed very poor, result, mechanical strength are very low.On the other hand, when using the aqueous resin of the latter, though can obtain the high density formed body, the environment when being subjected to being shaped (temperature, humidity) influence, the rerum natura of resin can produce responsive variation, and the fillibility to mould is reduced.
From the above-mentioned the 2nd and the 3rd shortcoming, for the target size generation error of magnet, that is, the precision of size is very poor, and its problem is the shape stability shortcoming.Especially, this shortcoming is the most remarkable when small-sized magnet is shaped.
Because the error of this size is very big, think the target size of guaranteeing final magnetic product, after roughly being shaped according to target size, essential by secondary operations such as cutting, grindings with the adjustment size.In view of the above, cause the increase operation, and, increased manufacturing expense owing to, therefore reduced production performance because of processing produces bad material.
The present inventor find out one of reason that above the 1st～3rd shortcoming occur be mixture manufacture method, create conditions, the temperature conditions when being shaped, the cooling condition after being shaped etc. all are not suitable for.
Therefore, the purpose of this invention is to provide, be easy to make the rare-earth adhesive magnet of formability, mechanical property, magnetic characteristic, excellent size stability, the manufacture method of rare-earth adhesive magnet, and the composition used of rare-earth adhesive magnet with low porosity.
Disclosure of an invention
The present invention utilizes binder resin the rare earth element magnet powder to be carried out the method for bonding manufacturing rare-earth adhesive magnet.The manufacture method feature of this rare-earth adhesive magnet is to comprise following operation.Promptly; above-mentioned rare earth element magnet powder and above-mentioned binder resin are mixed; the operation of mixing manufacturing mixture, this mixture is carried out granulation or whole grain make the operation of coccoid, use above-mentioned coccoid; make above-mentioned binder resin softening or form under the 1st temperature of molten condition, carrying out the operation of press molding and under pressurized state, be cooled to be lower than at least operation under the 2nd temperature of above-mentioned the 1st temperature.
According to this method can provide that porosity is low, the rare-earth adhesive magnet of formability, mechanical property, magnetic characteristic, excellent size stability.Particularly just can obtain such characteristic with a spot of binder resin.
Above-mentioned binder resin is thermoplastic resin preferably.
In view of the above, the porosity in better, the magnet of formability is lower.
Above-mentioned mixing, be preferably under the above temperature of the heat distortion temperature of above-mentioned binder resin, and the surface of above-mentioned rare earth element magnet powder is formed by fusion or softening binder resin composition under the state of coating and carries out.
In view of the above, can improve mixing efficient, evenly mixing owing to carrying out, so can reduce porosity.
In the said mixture, the content of rare earth element magnet powder is preferably 90～99 (weight) %.
In view of the above, make that the shared ratio of binder resin seldom can further improve magnetic characteristic in the magnet.
In addition, preferably contain antioxidant in the said mixture.
In view of the above, can suppress oxidation, the deterioration, rotten of manufacture process middle rare earth class ferromagnetic powder and binder resin, thereby improve magnetic characteristic.
The average grain diameter of above-mentioned coccoid is preferably 0.01～2mm.
In view of the above, can guarantee low porosity, and the quantitative property when improving feed, can provide dimensional accuracy high rare-earth adhesive magnet.
And above-mentioned the 2nd temperature is the fusing point or the heat distortion temperature of above-mentioned binder resin preferably.
Under the above-mentioned pressurized state, the pressure during cooling keeps constant at least during above-mentioned the 1st temperature arrives the 2nd temperature.
According to such formation, improving dimensional accuracy and reduce porosity can be more remarkable.
The present invention utilizes binder resin the rare earth element magnet powder to be carried out the method for bonding manufacturing rare-earth adhesive magnet.
The manufacture method of rare-earth adhesive magnet, feature are mixture or the mixing things that obtains above-mentioned rare earth element magnet powder and above-mentioned binder resin, and this mixture or mixing thing are carried out granulation or whole grain, form with this coccoid.
In view of the above, can provide that porosity is low, formability, excellent in magnetic characteristics, dimensional stability, the rare-earth adhesive magnet that promptly dimensional accuracy is high.Particularly, even also can obtain such characteristic with a spot of binder resin.
The maximum particle diameter of above-mentioned coccoid is preferably below the die gap minimum dimension of shaping dies.
Like this, the maximum particle diameter of above-mentioned coccoid is preferably in more than the 0.02mm.
And then the average grain diameter of above-mentioned coccoid is preferably 0.01～2mm.
According to such formation, can not only keep low porosity, and can further improve the dimensional accuracy of formed body.
Above-mentioned granulation or whole grain preferably utilize to pulverize and carry out.In view of the above, can be easy to carry out granulation or whole grain.
Preferably heat-treat after the above-mentioned shaping.
In view of the above, when binder resin is thermosetting resin, can make unhardened thermosetting resin sclerosis, when binder resin is thermoplastic resin, can strengthen its bonding force, can improve the mechanical strength of magnet.
In addition, the present invention makes the method for rare-earth adhesive magnet, still utilize the binder resin that forms by thermoplastic resin the rare earth element magnet powder to be carried out the method for bonding manufacturing rare-earth adhesive magnet, the feature of this method is to comprise following operation, promptly, soften or form under the 1st temperature of molten condition at above-mentioned binder resin, the composition that will contain above-mentioned rare earth element magnet powder and above-mentioned binder resin carries out the operation of press molding and be cooled to be lower than operation under the 2nd temperature of above-mentioned the 1st temperature at least under pressurized state.
Another method of making rare-earth adhesive magnet of the present invention is to utilize the binder resin that is formed by thermoplastic resin the rare earth element magnet powder to be carried out the method for bonding manufacturing rare-earth adhesive magnet, the feature of this method is to comprise following operation, promptly, under the temperature more than the heat distortion temperature of above-mentioned binder resin, the composition that will contain above-mentioned rare earth element magnet powder and above-mentioned binder resin carries out mixing operation, soften or form under the 1st temperature of molten condition at above-mentioned binder resin, above-mentioned mixing composition is carried out the operation of press molding, with under pressurized state, be cooled to be lower than the operation under the 2nd temperature of above-mentioned the 1st temperature at least.
According to these the present invention, can provide that porosity is low, the rare-earth adhesive magnet of formability, mechanical property, magnetic characteristic, excellent size stability.Particularly, promptly use a spot of binder resin, also can obtain such characteristic.
Above-mentioned the 2nd temperature is the fusing point or the heat distortion temperature of above-mentioned binder resin preferably.
Like this, the difference of above-mentioned the 1st temperature and the 2nd temperature is preferably in more than 20 ℃.
Constitute according to these, the raising of porosity reduction and dimensional accuracy is more remarkable.
Cooling under the above-mentioned in addition pressurized state under the pressure condition in the time of had better not removing above-mentioned press molding, is carried out continuously.
Forming pressure during for above-mentioned press molding, the pressure when preferably cooling off down with pressurized state is identical or be lower than this pressure.
Pressure during cooling under the above-mentioned pressurized state preferably remains to the fusing point of above-mentioned binder resin always.
Constitute according to these, the cooling advantage under the pressurized state can more effectively be brought into play, and can reduce porosity more and improve dimensional accuracy.
Cooling rate when above-mentioned pressurized state cools off down is preferably 0.5～100 ℃/second.
In view of the above, do not reduce productivity, and can keep very high mechanical strength and dimensional accuracy.
Forming pressure during above-mentioned press molding is preferably in 60kgf/mm 2Below.
By under low like this forming pressure, being shaped, can alleviating burden, and make easily shaping dies and forming machine.
Rare-earth adhesive magnet composition of the present invention, it is characterized in that utilizing binder resin that the rare earth element magnet powder is carried out in conjunction with the rare-earth adhesive magnet composition of making rare-earth adhesive magnet, and be the coccoid that mixture or mixing thing by rare earth element magnet powder and binder resin form, and the average grain diameter of this coccoid is 0.01～2mm.
Rare-earth adhesive magnet composition of the present invention, it is characterized in that utilizing binder resin to carry out the rare earth element magnet powder bonding, make the rare-earth adhesive magnet composition of rare-earth adhesive magnet again by compression molding, and be the coccoid that mixture or mixing thing by rare earth element magnet powder and binder resin form, and its maximum particle diameter is below shaping dies die gap minimum dimension.
By using these rare-earth adhesive magnet compositions, can produce at an easy rate that porosity is low, the rare-earth adhesive magnet of formability, mechanical property, magnetic characteristic, excellent size stability.Particularly, even with a spot of binder resin, also can obtain these characteristics.
The maximum particle diameter of above-mentioned coccoid is preferably in more than the 0.02mm.Can suppress the increase of porosity in view of the above.
Have again, the present invention is the rare-earth adhesive magnet of making by hot forming, and the thermoplastic resin of softening or molten condition will be shaped the time, under pressurized state, be cooled under the temperature below the forming temperature, again with the rare earth element magnet powder-stuck together by the above-mentioned thermoplastic resin that solidifies, and its porosity is below 4.5vol%, as the rare-earth adhesive magnet of feature.
The rare-earth adhesive magnet that the present invention still utilizes hot forming to make, and the thermoplastic resin of softening or molten condition in the time of will being shaped, under pressurized state, be cooled to below its heat distortion temperature or under the temperature below the fusing point, again with the rare earth element magnet powder-stuck together by the above-mentioned thermoplastic resin that solidifies, and, its porosity is below 4.0vol%, as the rare-earth adhesive magnet of feature.
The present invention also is to use the coccoid that is made by granulating working procedure, and rare-earth adhesive magnet by the hot forming manufacturing, the thermoplastic resin of softening or molten condition in the time of will being shaped again, under pressurized state, be cooled to below its heat distortion temperature or under the temperature below the fusing point, by the above-mentioned thermoplastic resin that solidifies together with the rare earth element magnet powder-stuck, and its porosity is below 4.0vol%, as the rare-earth adhesive magnet of feature.
Can provide the rare-earth adhesive magnet of formability, mechanical property, magnetic characteristic, excellent size stability according to these the present invention, particularly, even also can obtain these characteristics with the small number of bonded resin.
In the magnet, the content of above-mentioned rare earth element magnet powder is preferably 92.0～99.0wt%.
In view of the above, the shared ratio of binder resin is few more in the magnet, and the magnetic characteristic that obtains is high more.
Rare-earth adhesive magnet of the present invention, maximum magnetic flux energy product (BH) max is preferably in more than the 6MGOe when being shaped in no magnetic field.
Rare-earth adhesive magnet of the present invention, maximum magnetic flux energy product (BH) max is preferably in more than the 12MGOe when being shaped in magnetic field.
By having high like this magnetic characteristic, when for example rare-earth adhesive magnet of the present invention being used for motor, can obtain high performance motor.
The optimal morphology that carries out an invention
Below be elaborated with composition and rare-earth adhesive magnet with regard to manufacture method, the rare-earth adhesive magnet of rare-earth adhesive magnet.
The manufacture method of rare-earth adhesive magnet of the present invention mainly comprises following operation.
＜1〉the rare-earth adhesive magnet manufacturing of composition
At first, make rare-earth adhesive magnet with composition (being designated hereinafter simply as " composition ").Said composition mainly is made of rare earth element magnet powder and binder resin (adhesive).Preferably contain antioxidant, also can add other additive as required.These various constituents for example, use mixer such as Henschel or mixer to mix, and then carry out following mixingly, obtain mixing thing.
Below describe about these various constituents.
1. rare earth element magnet powder
Preferably constitute as the rare earth element magnet powder by the alloy that contains rare earth element and transition metal, especially preferred following [1]～[5].
[1] be based on the rare earth element R of Sm and based on the transition metal of Co as the alloy magnetic powder end of basis (below be called R-Co be alloy).
[2] be to be main transition metal and B as the alloy magnetic powder end of basis (below be called R-Fe-B be alloy) with R (still, R contains at least a in the Y rare earth element) and Fe.
[3] be as the alloy magnetic powder end of basis (below be called R-Fe-N be alloy) based on the calking element of the transition metal of rare earth element R, the Fe of Sm and N.
[4] be with R (but R is at least a kind that contains in the Y rare earth element) and transition metal such as Fe as basis, have mutually alloy magnetic powder end of nano-scale magnetic (below be called " nanocrystal magnet ").
[5] be to mix in the composition of above-mentioned [1]～[4] at least 2 kinds magnetic alloy powder.At this moment the advantage of each ferromagnetic powder of mixing can be had concurrently, and better magnetic characteristic can be easily obtained.
As R-Co is the representative of alloy, and specifiable have a SmCo 5, Sm 2TM 17(still, TM is the transition metal based on Co).
As R-Fe-B is the representative of alloy, the specifiable Nd-Fe-B of having be alloy, Pr-Fe-B be alloy, Nd-Pr-Fe-B be alloy, Ce-Nd-Fe-B be alloy, Ce-Pr-Nd-Fe-B be alloy, in these displacement of other transition metal such as the also available Co of the part of Fe, Ni or the like.
As R-Fe-N is the representative of alloy, and specifiable have Sm 2Fe 17Alloy carries out the Sm that nitrogenize is made 2Fe 17N 3
As what the above-mentioned rare earth element in the ferromagnetic powder can be enumerated Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Ib, Dy, Ho, Er, Tm, Yb, Lu, cerium lanthanum (mish metals) etc. are arranged.Can contain in these more than a kind or 2 kinds.As above-mentioned transition metal, that can enumerate has Fe, Co, a Ni etc., and can contain in these more than a kind or 2 kinds.In order to improve magnetic characteristic, in the ferromagnetic powder, can contain B, Al, Mo, Cu, Ga, Si, Ti, Ta, Zr, Hf, Ag, Zn etc. as required.
The average grain diameter of ferromagnetic powder though there is not particular determination, is preferably about 0.5～100 μ m, and is better about 1～50 μ m.In addition, the particle diameter of ferromagnetic powder etc. for example can utilize F.S.S.S (Fischer Sub-Sieve Sizer) method to measure.
The particle size distribution of ferromagnetic powder both can be even, can have dispersion (having discrete) to a certain degree again, still, says as later, and for obtaining good formability with a spot of binder resin when being shaped, preferably the back is a kind of.In view of the above, the bonded magnet that obtains can further reduce its porosity.In addition, during for above-mentioned [5], for each composition of mictomagnet powder, its average grain diameter can be different.
The manufacture method of ferromagnetic powder does not have particular determination, for example following any can, make alloy pig by the fusion casting, again this alloy pig is ground into suitable granularity (further classification), and obtains; To be used to make the chilling strip manufacturing installation of non-crystaline amorphous metal, make banded chilling thin slice (having gathered a lot of fine crystals), more this thin slice (strip) is ground into suitable granularity (further classification), and obtains.
Above ferromagnetic powder preferably is approximately 90～99wt% at the content of composition, and about 92～99wt% is better, and about 95～99wt% is especially good.When ferromagnetic powder content is very few, can not improve magnetic characteristic (maximum magnetic flux energy product), and dimensional accuracy also there is the trend of reduction.When ferromagnetic powder content was too much, correspondingly binder resin content tailed off, and formability reduces.
2. binder resin (adhesive)
As binder resin (adhesive), can use thermoplastic resin or thermosetting resin.As binder resin, when using thermoplastic resin,, more help obtaining the magnet of low porosity than using thermosetting resin.And among the present invention, the temperature conditions when being shaped according to aftermentioned, cooling condition can be realized lower porosity.
As thermoplastic resin, polyamide (example: nylon 6 is for example arranged, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66), the thermoplasticity polyimide resin, liquid crystal polymers such as aromatic polyester resin, polyhydroxyether resin, polyphenylens sulfide resin, polyvinyl resin, acrylic resin, vistanexes such as ethylene-vinyl acetate copolymer, the sex change vistanex, polyether resin, polyacetal resin etc., or based on their copolymer, mixture, polymer alloy etc., can use wherein a kind, or mix more than 2 kinds and use.
In these,, mechanical strength high consideration good from formability is preferably based on polyamide or its copolymer, consider from improving thermal endurance, preferably based on liquid crystal polymer, polyphenylens sulfide resin, formability and expense are low to be considered from being easy to, preferably based on polyolefin.The mixing property of these thermoplastic resins and ferromagnetic powder is fabulous.
Used thermoplastic resin, fusing point are preferably in more than 120 ℃, 122 ℃～400 ℃ better, 125 ℃～350 ℃ especially good.When fusing point was lower than above-mentioned lower limit, the thermal endurance of magnet formed body reduced, and was difficult to guarantee enough temperature characterisitics (magnetic or machinery).When fusing point surpassed above-mentioned higher limit, the temperature during shaping improved, and ferromagnetic powder etc. are easy to produce oxidation.
For further improving formability, the mean molecule quantity of used thermoplastic resin (degree of polymerization) is preferably about 10000～60000, and about 12000～35000 is better.
As thermosetting resin, epoxy resin, phenol resin, urea resin, melamino-formaldehyde resin, polyester (unsaturated polyester (UP)) resin, polyethers (example: the polyethers nitrile) resin, polyurethane resin etc. are for example arranged, can use wherein a kind, or mix more than 2 kinds and use.
In these, consider, preferably use epoxy resin, phenol resin from the angle that improves formability, mechanical strength height, good heat resistance more significantly.Epoxy resin is especially good.The mixing property of these thermosetting resins and ferromagnetic powder is fabulous.
In addition, thermosetting resin, though add with unhardened state, its form at room temperature is that arbitrary form of solid-state (Powdered), liquid, semi liquid state all can.
The content of above binder resin in composition, better about 1～8wt% about preferred 1～10wt%, especially good about 1～5wt%.When binder resin content is too much, can not obtain the raising of magnetic characteristic (particularly maximum magnetic flux energy product), and dimensional accuracy also there is reduction trend.When the content of binder resin was very few, formability reduced.
3. antioxidant
Antioxidant is when making composition, for prevent rare earth element magnet powder oxidation deterioration and binder resin oxidation deterioration (metal ingredient of rare earth element magnet powder is owing to play the effect of catalyst, and produce), the additive that adds in said composition.The interpolation of this antioxidant both can prevent the oxidation of rare earth element magnet powder, can improve the magnetic characteristic of magnet again, simultaneously, when composition is mixing, can improve the thermal stability when being shaped, just can guarantee to obtain good formability, play an important role with a spot of binder resin.
This antioxidant when being shaped when mixing and with magnet, volatilizees, and is rotten, so in the rare-earth adhesive magnet of manufacturing, still have a part with Restzustand.
As antioxidant, every any antioxidant that can obtain to prevent or suppress oxidation such as rare earth element magnet powder all can use, for example, more suitable used amine compound, amino acid based compound, nitrocarboxylic acid class, hydrazine compound, cyanogen compound, sulfide etc., for metal ion, particularly, generate the chelating agent of chelate compound for the Fe composition.In addition, for the kind of antioxidant, composition etc., only be defined in these.
When adding such antioxidant, the content of the antioxidant in the composition is preferably 0.1～2wt%, more preferably 0.5～1.5wt%.At this moment, the content of antioxidant with respect to the content of binder resin, is preferably 2～150%, and 30～100% is better.
In addition, among the present invention, the addition of antioxidant, according to the ratio of ferromagnetic powder and binder resin, cause that by ferromagnetic powder oxidation and resinous principle oxidation rotten degree decides, so, self-evident, below the lower limit of above-mentioned scope, or do not add yet and be fine.
The addition of above-mentioned binder resin and antioxidant for example can be taken pains by following form decision.
That is, binder resin is seldom the time, and is corresponding, increases the ferromagnetic powder amount, improved the viscosity of mixture when mixing, and increased mixing torque, because of heating, and impels the resin oxidation.At this moment, when anti-oxidation dosage seldom the time, can not fully restrain the resin oxidation, rise and produce mixing thing (resin melt) viscosity, mixing property, formability reduce, and can not get the magnet of low porosity, high mechanical properties, excellent size stability.And when anti-oxidation dosage is too much, reducing amount of resin accordingly, the mechanical strength of formed body demonstrates the trend of reduction again.
On the other hand, when binder resin is a lot, reduce the ferromagnetic powder amount accordingly, reduced the influence of ferromagnetic powder, so be difficult to cause the resin oxidation resin.Therefore, even with a spot of antioxidant, also can restrain the oxidation of resin.
Like this, binder resin content is many, and the content of antioxidant just can reduce, otherwise, binder resin content seldom, the content of antioxidant just must increase.
Therefore, in the composition, the total content of binder resin and antioxidant is preferably 1.0～8.0wt%, and 2.0～6.0wt% is better.By getting such scope, can improve the formability when being shaped, prevent the effect of oxidations such as ferromagnetic powder, help obtaining the magnet of low porosity, high mechanical properties, high magnetic characteristic.
4. other additive
In the composition, can add various additives as required, for example, plasticizer (as, aliphatic acid such as soaps such as zinc stearate, oleic acid), lubricant (as, various inorganic lubricants such as silicone oil, various wax, aliphatic acid, aluminium oxide, silicon dioxide, titanium dioxide), curing agent, hardening accelerator, other shaping additive etc.
The interpolation of plasticizer, owing to improved flowability when being shaped, binder resin that can less amount obtains same characteristic, also can carry out press molding with lower forming pressure.The interpolation of lubricant also is like this.The addition of plasticizer preferably is approximately 0.01～0.2wt%, and the addition of lubricant preferably is approximately 0.05～0.5wt%.
Above rare earth element magnet powder and binder resin, best and antioxidant also can mix with other additive as required, this mixture is made the composition of magnet shaping usefulness.At this moment, mixing can use mixers such as Henschel or mixer to carry out.
Preferably that said mixture is further mixing, make mixing thing, again it is made the composition of magnet shaping usefulness.At this moment, the mixing mixing rolls such as twin shaft extruding mixing roll, roll-type mixing roll, kneader that use carry out.
This mixing, though can carry out at normal temperatures, preferably, be more preferably under the temperature more than the fusing point of used binder resin and carry out carrying out more than the heat distortion temperature (measuring) of used binder resin or under the temperature more than the softening temperature with ASTM D648 method.
For example, as binder resin, when using polyamide (145 ℃ of heat distortion temperatures, 178 ℃ of fusing points), best melting temperature is about 150～280 ℃.As binder resin, when using phenol aldehyde type epoxy resin (80 ℃ of softening temperatures), best melting temperature is about 80～150 ℃.
Mixing time is according to the kind of binder resin, and mixing roll is typically about 3～120 minutes, preferably about 5～40 minutes with all conditions such as melting temperatures and different.
This is mixing to be that the surface of rare earth element magnet powder forms coated state fully by fusion or softening binder resin composition.Under above-mentioned melting temperature, carry out when mixing, for obtaining the mixing time of this state, can be according to conditions such as the mixing roll of the kind of binder resin and use, melting temperatures and different, be generally about 5～90 minutes best about 5～60 minutes.
Mixing by under such condition, carrying out, can improve melting efficiency.With compare when mixing under the normal temperature, can be more evenly mixing in shorter time.Simultaneously owing to be to carry out mixingly under the state that descends of the viscosity at binder resin, so form even coated state by binder resin around the rare earth element magnet powder, the porosity in the composition reduces, and the magnet mesopore rate that promptly makes reduces.
In addition, as binder resin, when several thermoplastic resins were mixed use, above-mentioned " heat distortion temperature of used viscosity resin (or fusing point) " for example, can convert in the following manner.
When the total of thermoplastic resin was got 1 weight portion, the amount of each thermoplastic resin was respectively A 1, A 2The An weight portion, the heat distortion temperature of each thermoplastic resin (or fusing point) is taken as T respectively 1, T 2During Tn, the heat distortion temperature of used thermoplastic resin (or fusing point) is with A 1T 1+ A 2T 2+ ... + AnTn represents.This conversion in following operation, is applicable to that also several thermoplastic resins mix when using.
＜2〉manufacturing of coccoid
With above-mentioned＜1〉in mixture or the mixing thing made carry out granulation or whole grain, manufacture the coccoid of regulation particle diameter.
The method of granulation or whole grain, though there is not particular determination, preferably by mixing thing etc. is pulverized.This pulverizing for example, can use ball mill, oscillating mill, disintegrating machine, jet mill, reciprocating type grinding machine etc. to carry out.
For example, also can use the comminutor of squash type comminutor one class to carry out, and then, also comminutor granulation and above-mentioned pulverizing combination can be carried out.
The adjustment of coccoid particle diameter can be carried out classification by using sieve etc.
Below do an argumentation with regard to the optimum size of this coccoid.
As coccoid, its maximum particle diameter is preferably below the minimum dimension of the mould die orifice hole space of coccoid (fill), and its maximum particle diameter is preferably in more than the 0.05mm more than 0.02mm.When the maximum particle diameter of coccoid surpasses the minimum dimension of mould die orifice hole, when coccoid is loaded in mould, directly loads with this state and to be difficult to, perhaps amount of fill is difficult to adjustment, and is unfavorable to the dimensional accuracy of raising bonded magnet.On the other hand, when the maximum particle diameter of coccoid was too small, the porosity of the bonded magnet that obtains was in rising trend.
As coccoid, its average grain diameter approximately can be 0.01～2mm, preferably approximately can be 0.02～2mm, and is better about 0.05～2mm.When the average grain diameter of coccoid surpassed 2mm, when particularly the magnet size of Xing Chenging is very little, that is, when the die orifice pore-size of shaping dies was very little, the amount of fill of coccoid in mould was difficult to carry out meticulous adjustment.Because quantitatively property is poor, so can not improve the dimensional accuracy of bonded magnet.On the other hand, the coccoid of the not enough 0.01mm of average grain diameter is made (granulation) difficulty, will take much more sometimes, and average grain diameter is when too small, and the porosity of the bonded magnet that obtains presents ascendant trend.
Such coccoid, particle diameter also allow deviation to a certain degree, but particle diameter is preferably uniform.Can increase filling density like this, obtain low porosity, the bonded magnet of high dimensional accuracy to mould.
In addition, said herein coccoid and the big block of particle diameter are distinguishing.
＜3〉press molding
Rare-earth adhesive magnet composition particularly uses above-mentioned＜2〉in the coccoid that obtains carry out press molding.Below describe with regard to representational compression molding.
At first,, take by weighing the coccoid of a certain amount of rare-earth adhesive magnet, be filled into the mould interior (die orifice) of compressing forming machine with composition for example by the stereometry and the gravimetry (weighing) of patterning method one class.
Then, with the coccoid that is filled in like this in the mould, in magnetic field (directional magnetic field, as 5～20kOe, orientation direction can be longitudinal and transverse, radially any one direction all can) or do not have and carry out compression molding in the magnetic field.
This compression molding can be adopted any in cold forming (near the shaping of normal temperature), cryogenic forming (be lower than under the softening temperature of binder resin, be shaped with warm-up mode), the hot forming, preferably hot forming.That is, by to processing such as shaping dies heat, the material temperature when being shaped is decided to be makes used binder resin, particularly thermoplastic resin softening or form the set point of temperature (the 1st temperature) of molten condition.
This 1st temperature is decided to be the heat distortion temperature of used binder resin or the temperature more than the softening temperature.And then, when used binder resin is thermoplastic resin, preferably get the above temperature of its fusing point, preferably get the temperature in the scope of fusing point about (fusing point+200) ℃, it is better to the temperature in (fusing point+130) ℃ left and right sides scope to get fusing point.
For example, when used thermoplastic resin is polyamide (fusing point: 178 ℃), about desirable 180-300 ℃ of best material temperature during shaping (the 1st temperature), and used thermosetting resin is when being phenol aldehyde type epoxy resin (softening temperature: 80 ℃), and the 1st best temperature can be taken as about 80～280 ℃.
By under such temperature, being shaped, can improve the flowability of moulding material in mould, cylindric, block is all needless to say more, the shape and size that just have cylindric (ring-type), tabular, the crooked thin-walled shape, small-sized, large-sized, low porosity such as tabular, high mechanical properties and have good stability, but all produce to the good quality and high output amount.
Forming pressure in the compression molding is at 60kgf/mm 2Below, be preferably in 2～50kgf/mm 2, 5～40kgf/mm more preferably 2Among the present invention,,, also can shape (figuration) bonded magnet for having above-mentioned advantage even with this lower forming pressure owing under above-mentioned the 1st temperature, be shaped.
Saidly be shaped under low like this forming pressure, its advantage is the burden that can alleviate shaping dies and forming machine, thereby has prevented the increase of maximizations such as shaping dies and forming machine power, and has prolonged useful life, so highly beneficial to making.
In addition, during cold forming, the forming pressure during compression molding is preferably got 20～100kgf/mm 2, better get 30～70kgf/mm 2
＜4〉cooling
When utilizing the hot forming press molding, subsequently, formed body is cooled off.This cooling is preferably in the set point of temperature (the 2nd temperature) that is cooled to be lower than above-mentioned the 1st temperature under the pressurized state.Below it is called
Figure C9719055300181
Add and depress cooling
Depress cooling by carrying out this adding, owing to can keep the low porosity state of when shaping former state, so can obtain the rare-earth adhesive magnet of low porosity, high dimensional accuracy, excellent in magnetic characteristics.
The 2nd temperature (remove and press temperature) can reduce the porosity of gained bonded magnet and improve dimensional accuracy, is preferably under the low temperature of trying one's best.Among the present invention, be preferably in fusing point or its following temperature of used binder resin (particularly thermoplastic resin), the heat distortion temperature of used binder resin (softening point) or its following temperature are better.
Above-mentioned the 1st temperature and the 2nd temperature poor is preferably in more than 20 ℃, and be better more than 50 ℃.This temperature difference is big more, and the raising effect of the reduction of porosity and dimensional accuracy is also big more.
In addition, when the ferromagnetic powder content in the composition is many,, also be easy to obtain the bonded magnet of low porosity even the 2nd temperature is set at higher.Therefore, for example, the ferromagnetic powder content in the mixing thing is as when 94wt% is above, even the 2nd temperature is decided to be near the temperature of used binder resin fusing point or the temperature more than the fusing point (～fusing point+10 ℃ about), also can makes porosity very low (4.5% below or below 4.0%).
Add and depress cooling, the pressurization during with press molding is in case after releasing or the mitigation, carry out all can.In order to simplify working process and to improve dimensional accuracy etc., the pressurization when preferably not removing press molding, and carry out continuously.
Add the pressure of depressing when cooling, can be certain, also can change, but will during above-mentioned the 1st temperature arrives above-mentioned the 2nd temperature, keep constant at least, be preferably in and keep constant during temperature is reduced to the fusing point of used binder resin (particularly heat distortion temperature) always.In view of the above, the raising effect of the reduction of porosity and dimensional accuracy obtains more significant performance.
In addition, when changing the pressure that adds when depressing cooling, for example, pressure can contain the form of the increase continuous or stage or minimizing.
Add the pressure (this pressure is time dependent average pressure) of depressing when cooling, preferably and the forming pressure during press molding equates or it under, the pressure during press molding during at least with the fusing point that arrives used binder resin equates, can be better.During the fusing point of used binder resin is cooled to heat distortion temperature is the occasion of pressurization cooling always, pressure therebetween, the forming pressure when preferably getting press molding about 40～100%, about 50～80% better.In view of the above, the raising effect of the reduction of porosity and dimensional accuracy can obtain bringing into play more significantly.
In addition, among the present invention, depress cooling back (remove and press the back) and also can proceed cooling adding at non-pressurised (under the normal pressure) down.In case cool off under non-pressurised,, can add once again to depress and cool off by continuing this process or heat treatment process described later.
Add the cooling rate of depressing when cooling (cooling rate is the mean value when changing in time),, preferably 0.5～100 ℃/second, be more preferably 1～80 ℃/second though there is not particular determination.When cooling rate is too fast, be accompanied by cooling, because of contraction rapidly, and at the trickle crackle of the inner generation of formed body, the danger that brings mechanical strength to reduce.Have again,, from mould taking-up finished product the time,, be easy to produce strain and distortion, dimensional accuracy is reduced because stress is eased because of cooling increases internal stress.On the other hand,, will increase the cycle period that is shaped, productivity ratio is reduced when cooling rate is crossed when slow.
When proceeding to cool off after remove pressing, its cooling rate does not have particular determination, can adopt and above-mentioned identical cooling rate.
In addition, add and depress when cooling and remove cooling rate when pressing the back cooling, also can be certain separately, also can change separately.
In addition, in this operation, cooling means for example has the combination of natural air cooling, forced air-cooling, water-cooled, oil cooling, water-cooled and air cooling cold etc., and which kind of method all can adopt.
＜5〉heat treatment
Above-mentioned＜3〉in, when carrying out cold forming, do not carry out above-mentioned＜4〉cooling.At this moment, as required,, implement heat treatment (baking) for the formed body that obtains.This heat treatment can or continue to carry out after the cooling behind hot forming, low warm forming.
This heat treated the 1st purpose is when binder resin is thermosetting resin, to make its thermmohardening.The 2nd purpose is, is softening or fusion with binder resin, strengthens bonding force by binder resin, to improve mechanical strength.
Be the heat treatment of the 1st purpose, binder resin be heated to the temperature more than its hardening temperature, its heating time is long, about for example 30 minutes～4 hours.
Be the heat treatment of the 2nd purpose, needless to say more when being configured as cold forming, can when above-mentioned hot forming and low warm forming, carry out, can bring into play its effect.The heat treatment of this moment is that binder resin is heated to temperature more than its softening point, preferably is heated to the above temperature of fusing point, and its heating time is shorter, for example, and about 1～30 minute.
Heat treatment of this operation and above-mentioned＜3〉operation carries out repetition, perhaps, in above-mentioned＜3〉carry out continuously in the operation, also can be in above-mentioned＜4〉carry out continuously in the operation.
In addition, this heat treated carrying out obviously, except that the above-mentioned the 1st and the 2nd purpose, also comprises other purpose.
As the above rare-earth adhesive magnet of making of the present invention, has following good characteristic.That is, porosity is low, below 4.5vol%, is preferably in below the 4.0vol%, better below 3.0vol%.Like this, because porosity very low (=density is very high), so the mechanical strength height, good corrosion resistance, and, the dimensional accuracy height, during batch process, the deviation of size is also very little, and dimensional stability is very good.
And then, excellent in magnetic characteristics, particularly how much from the content of the composition of ferromagnetic powder, ferromagnetic powder, even etc. side's property magnet, also have good magnetic characteristic.
Rare-earth adhesive magnet of the present invention, the content of the rare earth element magnet powder in magnet is 92～99wt%, best 94～99wt%, more preferably 96～99wt%.When ferromagnetic powder content is very few, can not get the raising of magnetic characteristic (particularly maximum magnetic flux energy product), and the trend that has dimensional accuracy to reduce.When ferromagnetic powder content was too much, corresponding binder resin content can reduce, and formability reduces.
During the rare-earth adhesive magnet that is shaped in no magnetic field, maximum magnetic flux energy product (BH) max is preferably more than the 6MGOe, more preferably more than the 8MGOe.During the rare-earth adhesive magnet that is shaped in magnetic field, maximum magnetic flux energy product (BH) max is preferably in more than the 12MGOe, better more than 13MGOe.Have high like this magnetic characteristic, and the rare-earth adhesive magnet that dimensional accuracy is high when for example being applied to motor, can be brought into play very high performance.
In addition, the form of the rare-earth adhesive magnet that makes according to the present invention, size etc., though there is not particular determination,, for example,, can be cylindric, corner post shape, cylindric, circular-arc (watt shape), tabular, crooked arbitrary shape such as tabular about shape.Its size, can be from large-scale to subminiature arbitrary dimension.And the purposes of rare-earth adhesive magnet is not had particular determination yet.
Below specific embodiments of the invention are described.
Embodiment 1
Following ferromagnetic powder, binder resin (thermoplastic resin) and additive are mixed, carry out this mixture mixing again, mixing thing is carried out granulation (whole grain), obtain shot-like particle, again this shot-like particle is loaded in the mould of make-up machine, in no magnetic field, carry out compression molding (hot forming), pressurized state bottom during shaping maintains this pressure bottom and cools off, curing by binder resin is bonded together ferromagnetic powder each other, makes rare-earth adhesive magnet (sample number: No.1a～9a).In addition, the content of each material, any one all shows with the scale in the mixing thing.Constitute
Nd-Fe-B based magnet powder: Nd 12.0Fe 77.8Co 4.3B 5.9,
96.0wt% (amount in the magnet is also roughly the same)
Thermoplastic resin: the A～G of record in the table 1 is respectively 2.8wt%
Antioxidant: hydrazine is an antioxidant, 1.2wt%
Mix: use the Henschel blender to mix
Mixing: as to use twin shaft extruding mixing roll mixing.Melting temperature is with reference to table 2.The screw rod revolution is
100～300rpm。Mixing time (residence time in the device) 5～15 minutes.
Granulation (whole grain): with mixing thing pulverizing, classification, being adjusted to average grain diameter is 0.8mm.
Be shaped: in the mould of packing under the shot-like particle room temperature, be heated to the forming temperature the (the 1st of regulation
Temperature) carries out press molding under.Forming temperature, forming pressure are with reference to table 2.
Cooling: pressurized state is kept on the limit, and the limit is cooled to remove presses temperature (the 2nd temperature), after pressing,
Be cooled to normal temperature again, take out sample.Cooling means adopts air cooling.Remove and press the temperature ginseng
According to table 2.Adding the cooling rate of depressing cooling is 1 ℃/second.
The formed products shape: cylindric (external diameter  30mm * internal diameter  28mm * high 7mm),
Tabular (20mm angle * thick 3mm) (mechanical strength is measured and used).
In addition, the heat distortion temperature in the table 1, below Ji ASTM D648 method is measured.
ASTM D648: with the two end supports of test film in oil bath, by the loading rod of central authorities,
Impose 4.6kgf/cm 2Bending stress, oil temperature is with 2 ℃ of/minute intensifications, mensuration is scratched
Curvature reaches the temperature of 0.254mm.
Measure its magnetic property (flux density Br, coercive force iHc, maximum magnetic flux energy product (BH) max), density, porosity, mechanical strength, corrosion resistance for gained rare-earth adhesive magnet, as shown in table 3 below.
In addition, measure the evaluation of the project of respectively measuring in the table 3 by the following method.
Magnetic property: after carrying out pulse and magnetic with 40kOe, under maximum externally-applied magnetic field 25kOe,
Utilize direct current magnetic-measurement machine to measure.Perhaps, by downcutting 5mm on the shaping sample
Behind the flat thin magnet of angle * thick 1mm, advance with test portion oscillating mode magnetometer (VSM)
Row is measured.
Density: utilize Archimedes's method (method in the water) to measure.
Porosity: form and the density measurement value of formed body is calculated by weighing.
Mechanical strength: utilize the punching press destructive test to measure.Testing machine uses (strain) island Tianjin system
Make made automatic recording instrument, utilize round punch (external diameter 3mm) with 1.0mm/min
Shear rate carry out.Test portion uses tabular magnet.
Corrosion resistance: the constant temperature and humidity cabinet that the magnet that is shaped is dropped into 80 ℃ of temperature, humidity 90%
In, measure the time that rust staining appears in magnet surface.From groove, took out in per 50 hours,
Observe the surface with light microscope (* 10 times).After 500 hours, become every again
Once observed in 500 hours.
As known from Table 3, according to the present invention, utilize the rare-earth adhesive magnet that thermoplastic resin makes as binder resin (sample No.1a～9a), any one is all irrelevant with low forming pressure, porosity is lower than 1%, obtain almost the high density bonded magnet the same with solid density, the result can obtain the high magnet of mechanical strength.
Even apply under the state that covers in that magnet surface is unreal, all have goodish corrosion resistance.The reason of inferring be since hole seldom, binder resin is coated on the surface of ferromagnetic powder equably.
For each magnet of sample No.1a～9a, take the electron micrograph (SEM) of the section of respectively cutting into slices, when observing, almost do not observe hole, so can confirm the binder resin that around ferromagnetic powder, is scattered here and there equably.
And then as can be known, flux density Br, coercive force iHc, maximum magnetic flux energy product (BH) max are very high, have good magnetic characteristic.
Embodiment 2
Following ferromagnetic powder and binder resin (thermosetting resin) are mixed, and carry out this mixture mixing, should mixing thing carry out granulation (whole grain) and obtain shot-like particle, again this shot-like particle is at room temperature packed in the mould of forming machine, in no magnetic field, carry out compression molding (cold forming or hot forming), afterwards, make binder resin sclerosis, make rare-earth adhesive magnet (sample No.10a～15a).Each content of material, any one all shows with the scale in the mixing thing.Constitute
Nd-Fe-B based magnet powder: Nd 12.0Fe 77.8Co 4.3B 5.9,
96.0wt% (amount in the magnet is roughly the same)
Thermosetting resin: put down in writing 4.0wt% (containing curing agent) in the table 4
Mix: when using under the room temperature hard resin, mix with V-Mixer.Use liquid under the room temperature
During the body resin, mix with mixer.
Mixing: as to use kneader mixing.Melting temperature is with reference to table 5, mixing roll revolution 50～250
Rpm, mixing time 30 minutes.
Granulation (whole grain): with mixing thing pulverize, classification, adjust average grain diameter at 0.8mm
Following grain.
Be shaped: in the mould of under the room temperature shot-like particle being packed into, press molding under the regulation forming temperature.
Forming temperature, forming pressure are with reference to table 5.
Cooling: be cooled to remove to press temperature, remove press after again cool to room temperature (except sample No.10a,
11a), take out sample.Cooling means adopts air cooling.Remove and press temperature with reference to table 5.
Cooling rate is 2 ℃/second.
Heat treatment: the half form product are packed in the thermostat, make the thermosetting resin sclerosis.The sclerosis bar
Part is with reference to table 4.
The formed products shape: cylindric (external diameter  30mm * internal diameter  28mm * high 7mm),
Tabular (20mm angle * thick 3mm) (mechanical strength is measured and used)
Surface treatment: for the corrosion resistance test sample, the formed body surface utilizes spray coating,
Bag is coated with the epithelium that epoxy resin forms the about 10 μ m of thickness.
Measure magnetic property (maximum magnetic flux energy product (BH) max), density, porosity, mechanical strength, corrosion resistance for the rare-earth adhesive magnet that obtains, shown in following table 6.The evaluation method of projects is identical with embodiment 1.
For each magnet of sample No.10a～15a, take the electron micrograph (SEM) of each disconnected tangent plane, observe, can confirm that particularly magnet central part hole is a lot, observe the binder resin composition that is scattered here and there equably around the ferromagnetic powder.
From table 5, table 6 as can be known, according to the present invention, use the rare-earth adhesive magnet that thermosetting resin makes as binder resin (sample No.10a～15a) particularly, be shaped relatively with thermoplastic resin, need high-pressure forming, porosity is also many than it, and minimum reaches about 5～6%.
Particularly, in the corrosion resistance test, must carry out surface treatment, this processing can be slight processing (a very thin epithelium), yet, even so slight surface treatment all demonstrates very good anti-corrosion.This is owing to reduced porosity, simultaneously, knows from above-mentioned SEM observed result, because the binder resin that evenly is scattered here and there around the ferromagnetic powder, coat film is coated on the magnet surface equably, so improved its adherence.And, owing to be slight surface treatment, so that the dimensional accuracy of integrated magnets can keep is very high.
Embodiment 3
Following ferromagnetic powder and binder resin (thermoplastic resin), additive are mixed, carry out this mixture mixing, should mixing thing carry out granulation (whole grain) and obtain shot-like particle, in the mould of the forming machine of again this shot-like particle being packed into, compression molding in magnetic field (hot forming).Pressurized state when being shaped maintains with depressing and cools off, and makes rare-earth adhesive magnet (sample No.16a～19a).Each content of material all shows with the scale in the mixing thing.Constitute
Sm-Co based magnet powder: Sm (Co Bal.Fe 0.32Cu 0.06Zr 0.016) 7.8,
95.0wt% (amount in the magnet is roughly the same)
Thermoplastic resin: PPS resin, 4.2wt%
Antioxidant: hydrazine is an antioxidant, 0.8wt%
Mix: use V-Mixer to mix.
Mixing: as to use various mixing rolls.Mixing condition is with reference to table 7.
Granulation (whole grain): with mixing thing pulverize, classification, adjust average grain diameter 0.8mm's
Particle.
Be shaped: in the mould of under the room temperature shot-like particle being packed into, be heated to the forming temperature the (the 1st of regulation
Temperature), the limit applies transverse magnetic field (15kOe) limit press molding.Forming temperature
320 ℃, forming pressure is 20kgf/mm 2
Cooling: keep pressurized state, be cooled to remove and press temperature (the 2nd temperature) 150 ℃, remove and press
After continue to be cooled to normal temperature, take out sample after taking off magnetic.Cooling means adopts air cooling.
Adding the cooling rate of depressing cooling is 5 ℃/second.
The formed products shape: (long 11mm * wide 8mm * high 7mm is by short transverse for cuboid
Directed.)。(be used for mechanical strength surveys tabular (20mm angle * thick 3mm)
Fixed).
For gained rare-earth adhesive magnet, measure magnetic property (maximum magnetic flux energy product (BH) max), density, porosity, mechanical strength, corrosion resistance, as shown in table 8.The evaluation method of projects is identical with embodiment 1.
As known from Table 8, (sample No.16a～19a), any one porosity all is lower than 1%, thereby has obtained highdensity bonded magnet, and the result is that mechanical strength and corrosion resistance are all very high according to rare-earth adhesive magnet of the present invention.
For each magnet of sample No.16a～19a, with the above-mentioned the same electron micrograph (SEM) of taking, when observing, almost do not observe hole, so can confirm the binder resin composition be evenly dispersed in ferromagnetic powder around.
And max is very high for maximum magnetic flux energy product (BH), has good magnetic characteristic.
Comparative example 1
Following ferromagnetic powder, binder resin (thermoplastic resin) and additive are mixed, this mixture is loaded in the mould of forming machine, (non-pressurised cooling down) cooled off in compression molding in magnetic field (hot forming), makes rare-earth adhesive magnet (sample No.20a, 21a).The content of each material is all with shown in the amount in the mixture.Constitute
Sm-Co based magnet powder: Sm (Co Bal.Fe 0.32Cu 0.06Zr 0.016) 7.8,
95.0wt% (sample No.20a),
96.0wt% (sample No.21a)
Thermoplastic resin: PPS resin, 4.2wt% (sample No.20a),
3.2wt% (sample No.21a)
Antioxidant: hydrazine is antioxidant, 0.8wt%
Mix: use V-Mixer to mix.
Be shaped: in the mould of under the room temperature mixture being packed into, be heated to the forming temperature of regulation, execute on the limit
Add transverse magnetic (15kOe) limit press molding.320 ℃ of forming temperatures are shaped and press
Power is 20kgf/mm 2
Cooling: after in shaping dies, taking off magnetic treatment, with sample by taking out in the shaping dies,
Under atmospheric pressure be cooled to normal temperature.Cooling means adopts air cooling.Cooling rate is
5 ℃/second.
Finished form: (long 11mm * wide 8mm * high 7mm, short transverse are for fixed for cuboid
To direction.), tabular (20mm angle * thick 3mm) (is used for mechanical strength
Measure).
The magnet of sample No.20a and 21a produces resin leakage when any one is shaped, because in the edge of formed products and the punching that end face sticks to forming machine, it is incomplete that formed products is produced, edge etc. produce broken, can not obtain desirable shape.
The part that is shaped is taken electron micrograph (SEM), and when observing, the binder resin composition disperses inhomogeneous, and ferromagnetic powder and binder resin partly are hybrid state.Can think and have a large amount of holes.
As mentioned above, the magnet of sample No.20a and 21a, any one also can not be measured to effective mechanical strength etc. owing to of poor quality.
Comparative example 2
Following ferromagnetic powder, binder resin (thermosetting resin) and additive are mixed.This mixture is loaded in the mould of forming machine, compression molding in magnetic field (cold forming) afterwards, makes the binder resin sclerosis, makes rare-earth adhesive magnet (sample No.22a).Each content of material is all with shown in the amount in the mixture.Constitute
Sm-Co. based magnet powder: Sm (Co Bal.Fe 0.32Cu 0.06Zr 0.016) 7.8,
96.0wt％
Thermosetting resin: bisphenol A-type novolac resin (60 ℃ of melt temperatures),
3.6wt% (containing curing agent)
Antioxidant: hydrazine is an antioxidant, 0.4wt%
Mix: use V-Mixer to mix.
Be shaped: in the mould of under the room temperature mixture being packed into, apply transverse magnetic field (15kOe) simultaneously
Press molding.Forming temperature is a room temperature, and forming pressure is 20kgf/mm 2
Heat treatment: after in mould, taking off magnetic treatment, in mould, take out, 170 ℃ * 4
Hour condition under heat-treat, thermosetting resin is hardened.
The formed products shape: (long 11mm * wide 8mm * high 7mm, short transverse is cuboid
Orientation direction.)，
Tabular (20mm angle * thick 3mm) (being used for mechanical strength measures).
The magnet of sample No.22a because at room temperature, uses the epoxy resin that is solid shape under the room temperature, mixture is formed, so the bonding force between powder is very weak, and resinous principle disperses also insufficient, also because after taking off magnetic, still residual in the powder have remaining flux, comes off the formed products incompleteness so produce ferromagnetic powder, problems such as edges broken can not obtain desirable shape.
Shaped portion is taken electron micrograph (SEM), and when observing, it is inhomogeneous to see that the binder resin composition disperses, and ferromagnetic powder part and binder resin partly are hybrid state.
As mentioned above, sample No.3a magnet is substandard products, also can not measure mechanical strength etc. effectively.
Embodiment 4
Following ferromagnetic powder (2 kinds), binder resin (thermoplastic resin) and additive are mixed, carry out this mixture mixing, again should mixing thing carry out granulation (whole grain) and obtain shot-like particle, this shot-like particle is loaded in the mould of forming machine and carries out compression molding (hot forming), pressurized state when being shaped maintains with depressing and cools off, and makes rare-earth adhesive magnet (sample No.23a～31a).The content of each material is all with shown in the amount in the mixing thing.Constitute
Sm-Co based magnet powder: Sm (Co 0.672Fe 0.22Cu 0.08Zr 0.028) 8.35,
70.5wt% (amount in the magnet is also roughly the same)
Sm-Fe-N based magnet powder: Sm 2Fe 17N 3, (amount in the magnet also for 23.5wt%
Roughly the same)
Thermoplastic resin: polyamide (nylon 12), 5.0wt%
Antioxidant: phenol is antioxidant, 1.0wt%
Mix: use the Henschel blender to mix.
Mixing: as to use twin shaft extruding mixing roll mixing.Melting temperature is 150～300 ℃.Screw rod
Revolution is 100～300rpm.Mixing time (residence time in the device) 10～
15 minutes.
Granulation (whole grain):, be adjusted into granularity shown in the table 9 by with mixing thing pulverizing, classification.
Be shaped: use cutting mode, at room temperature shot-like particle is packed in the mould, be heated to 220
℃ (the 1st temperature), the limit applies transverse magnetic field (15kOe) limit press molding.
Forming pressure is 10kgf/m 2
Cooling: keep pressurized state, be cooled to remove 100 ℃ of pressure temperature (the 2nd temperature), take out
Sample.Cooling means adopts water-cooled.Add the cooling rate of depressing cooling and be 20 ℃/
Second.
Formed products shape: tabular (wide 15mm * thick 2.5mm * high 5mm, short transverse
Be orientation direction)
For gained rare-earth adhesive magnet, measure the weight, density, porosity of magnet, highly, as shown in following table 9.
As known from Table 9,, obtain good quantitative property, obtain the high bonded magnet of low porosity and dimensional accuracy by setting the particle diameter of shot-like particle.Sample number No.23a～30a particularly, the particle diameter of shot-like particle is 0.01～2mm scope, can obtain ultralow porosity (below 1.5%, particularly below 1%) and very high dimensional accuracy (scale error ± 5/100mm in) simultaneously.
Embodiment 5
Following ferromagnetic powder, binder resin (thermoplastic resin) and additive are mixed, carry out this mixture mixing again, should mixing thing carry out granulation (whole grain) and obtain shot-like particle, again this shot-like particle is packed in the mould of forming machine, in magnetic field, carry out compression molding (hot forming), pressurized state when being shaped maintains with depressing, and cooling makes rare-earth adhesive magnet (sample No.32a～42a).The content of each material is all with shown in the amount in the mixing thing.Constitute
Nd-Fe-B based magnet powder: Nd 12.6Fe 69.3Co 12.0B 6.0Zr 0.1, 97.0wt%
(amount in the magnet is also roughly the same)
Thermoplastic resin: A in the table 1 or F are respectively 1.5wt%
Antioxidant: hydrazine is antioxidant, 1.4wt%
Lubricant: zinc stearate, 0.1wt%
Mix: use the Henschel blender to mix.
Mixing: as to use twin shaft extruding mixing roll mixing.150～350 ℃ of melting temperatures.Screw rod changes
Several 100～300rpm.Mixing time (residence time in the device) 5～10 minutes
Clock.
Granulation (whole grain): by with mixing thing pulverizing, classification, to adjust to average grain diameter be 0.3mm
Granularity.
Be shaped: in the mould of under the room temperature shot-like particle being packed into, be heated to forming temperature shown in the table 10
(the 1st temperature), limit apply radial magnetic field (15kOe) limit press molding.Become
Shape pressure is 15kgf/mm 2
Cooling: keep pressurized state, be cooled to remove and press temperature (the 2nd temperature) 100 ℃, carry out
After taking off magnetic treatment, remove pressure, be cooled to normal temperature again, take out sample.Cooling side
Method adopts water-cooled, and adding the cooling rate of depressing cooling is 30 ℃/second.
Finished form: cylindric (external diameter  20mm * internal diameter  18mm * high 5mm, highly
Pressurize on the direction), tabular (120mm angle * thick 3mm) (is used for machinery
Strength detection)
For gained rare-earth adhesive magnet, measure magnetic characteristic (maximum magnetic flux energy product (BH) max), density, porosity, mechanical strength, as shown in table 10 below.The evaluation method of projects is identical with embodiment 1.
As the sample No.32a～42a in the table 10, when the shaping temperature when the heat distortion temperature of binder resin is above, binder resin becomes softening or molten condition during shaping, so can be shaped.
Particularly sample No.33a～36a, 40a～42a, forming temperature are when the fusing point of binder resin is above, and the magnet porosity that obtains can further reduce, and magnetic property is also higher.
Embodiment 6
Following ferromagnetic powder, binder resin (thermoplastic resin) and additive are mixed, carry out this mixture mixing again, should carry out granulation (whole grain) by mixing thing, obtain shot-like particle, this shot-like particle at room temperature is loaded in the mould of forming machine again, is shaped (hot forming) in no magnetic field lower compression, the pressurized state during with shaping maintains with depressing, cooling makes rare-earth adhesive magnet (sample No.43a～52a).The content of each material is all with shown in the amount in the mixing thing.Constitute
Nanocrystal Nd-Fe-B based magnet powder: Nd 5.5Fe 66B 18.5Co 5Cr 5, 98.0wt%
(amount in the magnet is also roughly the same)
Thermoplastic resin: A in the table 1 or G are respectively 1.0wt%
Antioxidant: hydrazine is antioxidant 1.0wt%
Mix: use the Henschel blender to mix
Mixing: as to use twin shaft extruding mixing roll mixing.Melting temperature is 150～350 ℃.Screw rod
Revolution 100～300rpm.Mixing time (residence time in the device) 10～15
Minute.
Granulation (whole grain): by being 0.1mm with mixing thing pulverizing, classification, adjustment average grain diameter
Granularity.
Be shaped: shot-like particle is packed in the mould, be heated to the forming temperature (the 1st temperature) of regulation,
Carry out press molding.Forming temperature is 200 ℃ (Resin A) and 300 ℃ of (trees
Fat G), forming pressure is 25kgf/mm 2
Cooling: keep pressurized state, be cooled to removing shown in the table 11 and press temperature (the 2nd temperature),
Take out sample.Cooling means adopts water-cooled.Adding the cooling rate of depressing cooling is 50
℃/second.
Finished form: cylindric (external diameter  10mm * internal diameter  7mm * high 7mm is at height
Pressurize on the direction)
For the rare-earth adhesive magnet that obtains, measure magnet performance (maximum magnetic flux energy product (BH) man), density, porosity, external diameter, as shown in table 11 below.The evaluation method of projects is identical with embodiment 1.
As the sample No.43a～52a in the table 11, press below the fusing point of temperature at binder resin when removing, or the difference of remove pressing temperature and forming temperature is more than 20 ℃ the time, the magnet that obtains, porosity are very low, density is very high, magnetic property is very high, dimensional accuracy also very high (scale error ± 5/100mm in).Such characteristic is removed and is pressed temperature low more, can improve more.
Particularly sample No.46a, 47a, 50a, 51a, 52a press temperature when the heat distortion temperature of binder resin is following when removing, and can reach the density that almost approaches theoretical value, can give full play to the ferromagnetic powder characteristic, form the fabulous magnet of magnetic property.
Embodiment 7
Following ferromagnetic powder, binder resin (thermoplastic resin) and additive are mixed, this mixture is mixing, should carry out granulation (whole grain) by mixing thing, obtain coccoid, in the mould of the forming machine of again this coccoid at room temperature being packed into, compression molding in no magnetic field (hot forming), pressurized state during with shaping maintains with depressing, and cooling is by the curing of binder resin, ferromagnetic powder is bonded together to each other, makes rare-earth adhesive magnet (sample No.1b～6b).
Nd-Fe-B based magnet powder: Nd 12.0Fe 77.8Co 4.3B 5.9, 97wt% is (in the magnet
Amount roughly the same)
Polyamide (PA12): 178 ℃ of fusing points, 145 ℃ of heat distortion temperatures, 1.6wt%
Antioxidant: hydrazine is antioxidant 1.4wt%
Mix: use the Henschel blender to mix.
Mixing: as to use twin shaft extruding mixing roll mixing.150～250 ℃ of melting temperatures, screw rod changes
Several 100～250rpm.
Granulation (whole grain): mixing thing is pulverized, be adjusted into the granularity of average grain diameter 1mm.
Be shaped: after packing into composition (coccoid) in the mould, with mold heated to shown in the table 12
Temperature (the 1st temperature), with drift pressurization, forming pressure is 10kgf/mm 2
Cooling: keep pressurized state, cool off, under 100 ℃ (the 2nd temperature), remove pressure
Power is taken out sample.The cooling means air cooling.Add the cooling rate 0.5 of depressing cooling
℃/second.
The formed products shape: cylindric ( 10mm * high 7mm) and
Tabular (20mm angle * thick 3.0mm).
For gained rare-earth adhesive magnet, measure magnetic property (flux density Br, coercive force iHc, maximum magnetic flux energy product (BH) max), density, porosity, mechanical strength, shown in following table 12.In addition, the evaluation method of the project of respectively measuring in the table 12 is identical with embodiment 1.
As shown in Table 12, when the shaping temperature was very high, the bonded magnet that obtains presented the trend of high density, low porosity.As sample No.3b～6b, forming temperature is when the fusing point of used thermoplastic resin is above, and especially, porosity is low especially, and mechanical strength and magnetic property demonstrate very high value.
Embodiment 8
Ferromagnetic powder shown in the following table 13, binder resin (thermoplastic resin) and additive are mixed, carry out this mixture mixing, should carry out granulation (whole grain) by mixing thing again, obtain coccoid, this coccoid is at room temperature packed in the mould of forming machine, compression molding in no magnetic field (hot forming), pressurized state during with shaping maintains with depressing, cooling, curing by binder resin is bonded together ferromagnetic powder each other, makes rare-earth adhesive magnet (sample No.7b～31b).
Ferromagnetic powder: powder shown in the table 13 1～5, respectively be that (amount in the magnet also for 96.0wt%
Roughly the same)
Polyamide (PA12): 178 ℃ of fusing points, 145 ℃ of heat distortion temperatures, 2.55wt%
Antioxidant: hydrazine is antioxidant 1.4wt%
Other additive: higher fatty acids (stearic acid) 0.05wt%
Mix: use the Henschel blender to mix.
Mixing: as to use twin shaft extruding mixing roll mixing.150～250 ℃ of melting temperatures, screw rod change
Several 100～250rpm.
Granulation (whole grain): by being 0.5mm with mixing thing pulverizing, classification, adjustment average grain diameter
Granularity.
Be shaped: after packing into composition (coccoid) in the mould, be heated to 230 ℃ of (the 1st temperature
Degree), with drift pressurization, forming pressure 15kgf/mm 2
Cooling: keep cooling under the pressurized state, under temperature shown in the table 14 (the 2nd temperature), go
Fall pressure, take out sample.Cooling means adopts air cooling.Add the cooling of depressing cooling
Speed is 2 ℃/second.
Finished form: cylindric (external diameter  20mm * internal diameter  18mm * high 10mm).
In addition, the average grain diameter in the table 13, (Fisher Sub-Sieve Sizer) measures by the F.S.S.S. determination method.
To the rare-earth adhesive magnet that obtains, measure density, porosity, out of roundness (dimensional accuracy), shown in table 14,15.In addition, the evaluation of the project of respectively measuring in table 14, the table 15 is carried out by the following method.
Density: identical with embodiment 1
Porosity: identical with embodiment 1
Out of roundness: measure 10 points of formed products external diameter, press by the maximum and the minimum value of this measured value
Following formula is calculated.
Out of roundness=(maximum-minimum value)/2
Shown in table 14,15, for the ferromagnetic powder of each composition, temperature is pressed in removing when reducing cooling, and the density of gained bonded magnet increases, and porosity reduces, and folding is difficult to produce distortion when removing sample, thereby has improved out of roundness (dimensional accuracy).Removing during cooling presses temperature below used thermoplastic resin fusing point (178 ℃), when particularly heat distortion temperature (145 ℃) is following, obtains high out of roundness (dimensional accuracy).
Embodiment 9
Binder resin (thermoplastic resin) shown in following ferromagnetic powder, the following table 16 and additive are mixed, carry out this mixture mixing, should carry out granulation (whole grain) by mixing thing again, obtain coccoid, this coccoid is packed under room temperature in the mould of forming machine, compression molding in magnetic field (hot forming), pressurized state during with shaping maintains with depressing, cooling, curing by binder resin adheres to each other ferromagnetic powder, makes rare-earth adhesive magnet (sample No.32b～62b).
Ferromagnetic powder: Sm (Co 0.762Fe 0.22Cu 0.08Zr 0.028) 8.35, 96.5wt% is (in the magnet
Amount also roughly the same)
Thermoplastic resin: the A～G shown in the table 16, A+B, respectively be 2.3wt%
Antioxidant: phenol is antioxidant 1.2wt%
Mix: use the Henschel blender to mix.
Mixing: use twin shaft extruding mixing roll mixing, melting temperature is with reference to table 5.Screw rod revolution 100
～250rpm。
Granulation (whole grain): by mixing thing is pulverized, classification, the adjustment average grain diameter is 0.5mm
Granularity.
Be shaped: after under room temperature, packing into composition (coccoid) in the mould, mold heated is arrived
Temperature shown in the table 16 (the 1st temperature) is pressurizeed with drift.Forming pressure 10
Kgf/mm 2, apply radial magnetic field (directional magnetic field 15kOe) before the pressurization.
Cooling: keep pressurized state and cool off, in temperature shown in table 17～table 19 the (the 2nd
Temperature) under, take off magnetic treatment after, remove pressure, take out sample.Cooling side
Method adopts water-cooled, and adding the cooling rate of depressing cooling is 10 ℃/second.
Finished form: cylindric (external diameter  30mm * internal diameter  27mm * high 5mm).
In addition, the heat distortion temperature in the table 16 is measured with the method for above-mentioned ASTM D648.
For gained rare-earth adhesive magnet, measure density, porosity, out of roundness (dimensional accuracy), as shown in following table 17-table 18, table 19.In addition, the evaluation of the project of respectively measuring in the table 17,18,19 is carried out according to the foregoing description 1,8 identical methods.
Shown in table 17～19, for the thermoplastic resin of each composition, removing during along with cooling presses temperature to reduce, and the density of gained bonded magnet increases, and porosity reduces, and demonstrates the trend that out of roundness (dimensional accuracy) improves.Removing during cooling presses temperature below the fusing point of used thermoplastic resin, particularly when heat distortion temperature is following, can obtain high out of roundness (dimensional accuracy).
For each sample shown in table 17～19, measure magnetic property with above-mentioned same method, any one flux density Br is all more than 7.0kG, and coercive force iHc is more than 7kOe, and maximum magnetic flux energy product (BH) max and demonstrates very high value more than 13MGOe.
Embodiment 10
With ferromagnetic powder, binder resin (thermoplastic resin) and additive, form shown in the following table 20 and mix, carry out this mixture mixing, should carry out granulation (whole grain) by mixing thing again, obtain coccoid, this coccoid is loaded in the mould of forming machine, in no magnetic field lower compression shaping (hot forming), pressurized state when keep being shaped, and under uniform pressure until fusing point, afterwards, one side is reduced to pressure about 50%, cooling simultaneously, the curing by binder resin is bonded together ferromagnetic powder to each other, makes rare-earth adhesive magnet (sample No.63b～80b).Ferromagnetic powder amount and the value in the table 20 in the gained magnet are roughly the same.
Ferromagnetic powder: Nd 12.0Fe 77.8Co 4.3B 5.9
Polyamide (PA12): 178 ℃ of fusing points, 145 ℃ of heat distortion temperatures
Antioxidant: hydrazine is an antioxidant
Mix: use the Henschel blender to mix.
Mixing: as to use twin shaft extruding mixing roll mixing.100～250 ℃ of melting temperatures, screw rod changes
Several 100～250prm.
Granulation (whole grain): by mixing thing is pulverized, classification, the adjustment average grain diameter is 0.5mm
Granularity.
Be shaped: after under room temperature, packing into composition (coccoid) in the mould, mold heated is arrived
220 ℃ (the 1st temperature), with the drift pressurization, forming pressure is 20kgf/mm 2
The cooling: keep pressurized state (pressure reduces in time) and cool off, following table 21,
Under the temperature shown in the table 22 (the 2nd temperature), remove pressure fully, take out sample
Product.Cooling means adopts water-cooled.Add 50 ℃/second of cooling rates depressing cooling.
The formed products shape: watt shape (periphery radius of curvature R 8mm * interior all radius of curvature r7mm *
120 ° * high 8mm).
For gained rare-earth adhesive magnet, measure density, porosity, out of roundness (dimensional accuracy) and magnetic characteristic (maximum magnetic flux energy product (BH) max), as shown in table 21, table 22.
In addition, respectively measure the evaluation of project in table 21, the table 22, undertaken by the foregoing description 1,8 identical methods.
Shown in table 21, table 22, for each content of ferromagnetic powder, the step-down temperature during along with cooling reduces, and the density of gained bonded magnet increases, porosity reduces, demonstrate the trend that out of roundness (dimensional accuracy) improves.Removing during cooling presses temperature below the fusing point of used thermoplastic resin, particularly when heat distortion temperature is following, can obtain high out of roundness (dimensional accuracy).
Embodiment 11
Form with the raw material shown in the following table 23, additives such as ferromagnetic powder, binder resin (thermoplastic resin) and antioxidant are mixed, carry out this mixture mixing, should carry out granulation (whole grain) by mixing thing again, obtain coccoid, in the mould of the forming machine of again this coccoid being packed into, under no magnetic field or in magnetic field under room temperature, compression molding (hot forming), cooling make rare-earth adhesive magnet (sample No.1c～6c).Each condition in the manufacturing is as follows.
Mix: use the Henschel blender to mix.
Mixing: as to use twin shaft extruding mixing roll mixing.200～350 ℃ of melting temperatures, screw rod changes
Several 100～300rpm squeeze out the cylindric of  10mm, make long by 5～
The particle of 15mm.
Granulation: above-mentioned particle is pulverized, got the following powder of 1mm sieve mesh.Each sample is flat
All particle diameter is 0.2～0.8mm.
Be shaped: use hydraulic press.Forming temperature is with reference to table 24, forming pressure 10kgf/mm 2Become
The shape product are shaped as cylindric (external diameter  20mm * internal diameter  17mm * high 5mm)
Cooling: be cooled to normal temperature under the atmospheric pressure
For gained rare-earth adhesive magnet, measure flux density Br, coercive force iHc, maximum magnetic flux energy product (BH) max, density and porosity.The results are shown in table 24.
In addition, assay method is as follows.
Magnetic property: the sample by cutting 5mm angle on the shaping sample, carry out pulse with 40kOe and
Behind the magnetic, use test portion oscillating mode magnetometer (VSM) to measure.
Density measurement: identical with embodiment 1.
Porosity: identical with embodiment 1.
Comparative example 3
Form with raw material shown in the above-mentioned table 23, additives such as ferromagnetic powder and binder resin (thermoplastic resin) and antioxidant are mixed, carry out this mixture mixing, the mixing thing of graininess is packed in the mould of forming machine, compression molding in no magnetic field or in magnetic field (cryogenic forming), add and depress cooling, make rare-earth adhesive magnet (sample No.7c～12c).
The various conditions of making are as follows.
Mix: identical with the foregoing description 11.
Mixing: identical with the foregoing description 11.
Granulation: do not carry out
Be shaped: divided by forming temperature shown in the table 25, outside the forming pressure, other and embodiment
11 is identical.
Cooling: press temperature to remove shown in the table 25, add and depress cooling.In mould, take off magnetic
After the processing, remove pressure.
Forming results is as follows.
Sample No.7c～12c, above for 10mm * 5mm because the die gap minimum dimension of mould (magnet wall thickness) be 1.5mm, be difficult to this particle is packed in the mould, thus the one side of having to drift particle is pulverized, perhaps with the particle heating and melting.Use drift to divide on one side and be pressed into several times, otherwise can not form.For this reason, need spended time during shaping, forming period is very long, so be difficult to form with low expense.Also be difficult to control the loading in mould.Error with respect to target size (sample length) forming dimension is very big, and size stability is not good enough yet.
Sample No.7c～12c, any one forming temperature is lower than the heat distortion temperature of binder resin, no matter how high forming pressure is, porosity is all very high.
Embodiment 12
Following ferromagnetic powder, binder resin (thermoplastic resin) and additive are mixed, carry out this mixture mixing, should carry out granulation (whole grain) by mixing thing again, obtain coccoid, this coccoid is filled under room temperature in the mould of forming machine, compression molding in magnetic field (cold forming) is then implemented heat treatment, is cooled off, makes rare-earth adhesive magnet (sample No.13c).
Ferromagnetic powder: Nd 9.6Pr 2.4Fe 77.8Co 4.3B 5.9, (F.S.S.S. surveys average grain diameter 20 μ m
96.5wt% (amount in the magnet is roughly the same) calmly),
Binder resin: PPS (polyphenylene sulfide) resin, 2.3wt%
Additive: hydrazine is antioxidant 1.2wt%
Mix: identical with embodiment 11.
Mixing: identical with embodiment 11.
Granulation: above-mentioned particle is pulverized, got the following powder of 0.8mm sieve mesh, average grain diameter
Be 0.5mm.
Be shaped: use hydraulic press.Forming temperature is a room temperature.In the no magnetic field, forming pressure 70kgf/
mm 2。Be configured as the half form product.Finished form: cylindric (target size: outer
Footpath  25.00mm * internal diameter  23.00mm * high 10.00mm), die size:
The die gap of external diameter  24.35mm * internal diameter  22.40mm.
Heat treatment: 320 ℃ were heated 10 minutes down.Make resinous principle fusion, interlaminar resin bonding mutually.
Can improve mechanical strength.
For gained rare-earth adhesive magnet, size up precision, magnetic property, density, porosity are as follows.
Formed products size: external diameter 224.98mm * internal diameter  23.01mm * high 10.02mm (n
=10 mean value), the error σ of (length)=0.02 highly
Magnetic property: Br=6.88kG, iHc=9.63kOe, (BH) max=9.6MGOe
Density: 6.08g/cm 3
Porosity: 2.06%
(mensuration of magnetic property after carrying out pulse and add magnetic with 40kOe, applies under the 25kOe of magnetic field in maximum, utilizes direct current magnetic-measurement machine to measure.)
Among this embodiment 12, when loading (feed) in mould, amount of fill can be carried out careful adjustment, and the result can confirm to obtain high dimensional accuracy.And magnetic property is also good, and porosity is also very low.
Comparative example 4
Following ferromagnetic powder, binder resin (thermoplastic resin) and additive are mixed, carry out this mixture mixing, again the mixing thing of graininess is packed in the mould of forming machine, compression molding in magnetic field (cold forming), then implement heat treatment, cooling makes rare-earth adhesive magnet (sample No.14c).
Ferromagnetic powder: Nd 9.6Pr 2.4Fe 77.8Co 4.3B 5.9, (F.S.S.S. surveys average grain diameter 20 μ m
96.5wt% calmly),
Binder resin: PPS (polyphenylene sulfide) resin, 2.3wt%
Additive: hydrazine is antioxidant 1.2wt%
Mix: identical with embodiment 11.
Mixing: identical with embodiment 11.
Granulation: do not carry out
Be shaped: identical with embodiment 12.
Heat treatment: identical with embodiment 12.
For gained rare-earth adhesive magnet, the size up precision is as follows.
Formed products size: external diameter  24.98mm * internal diameter  23.01mm * high 9.52mm (n
=10 mean value), Gao Du error σ=0.90
In this comparative example 4, the same with above-mentioned comparative example 3 owing to do not carry out granulation, the height of feed instability, particularly formed products is easy to generate error in mould, is difficult to carry out stable shaping.In order to carry out feed, must Yi Bian clamp-on, curring time be increased on one side with pulverized particles about the drift.And for easily producing the drift damage in the grain.
Embodiment 13
Following ferromagnetic powder, binder resin (thermosetting resin) and additive are mixed, again this mixture is carried out granulation (whole grain), obtain coccoid, this coccoid is packed under room temperature in the mould of forming machine, compression molding in magnetic field (hot forming), then implement heat treatment, make hardening of resin, cooling makes rare-earth adhesive magnet (sample No.15c) subsequently.
Ferromagnetic powder: Sm (Co 0.672Fe 0.22Cu 0.08Zr 0.028) 8.35, average grain diameter 20 μ m
(measuring), 97.5wt% (amount in the magnet is roughly the same) with F.S.S.S.
Binder resin: phenol resin 2.45wt%+ organic solvent, resin at room temperature are solid, and be soft
Change 60 ℃ of temperature.
Additive: zinc stearate 0.05wt%
Mix: use omnipotent mixer, mix on evaporation organic solvent limit, limit.
Granulation:, get the following powder of 180 μ m sieve meshes by grinding fragmentation.Average grain diameter is
100μm。
Be shaped: use hydraulic press.80 ℃ of forming temperatures, directional magnetic field 17kOe (transverse magnetic
The field), forming pressure 30kgf/mm 2Be processed into the dumming product.The formed products shape
Be a watt shape (target size: periphery radius of curvature R 15.00mm * interior all curvature half
R12.00mm * 120 °, footpath * high 8.00mm).Footpath direction directional magnetic field.Add
After the pressure, in mould, take off magnetic.
Die size: R14.70mm * r11.80mm * 120 °
Die gap heat treatment: 180 ℃ were heated 2 hours down.
For gained rare-earth adhesive magnet, size up precision, magnetic property, density, porosity are as follows.
Formed products size: R15.03mm * r12.01mm * 120 ° * 17.98mm (n=
10 mean value), height error σ=0.015
Magnetic property: Br=7.81kG, iHc=7.10kOe, (BH) max=13.6MGOe
Density: 7.11g/cm 3
Porosity: 4.63%
(magnetic property is measured, and behind watt flat thin magnet at shape magnet cutting 5mm angle, uses
VSM measures.)
In this embodiment 13, when in mould, loading (feed), can careful adjustment amount of fill, the result can confirm to obtain high dimensional accuracy.And, having excellent magnetic characteristics, porosity is very low.
Comparative example 5
Following ferromagnetic powder, binder resin (thermosetting resin) and additive are mixed, this mixture is packed under room temperature in the mould of forming machine, compression molding in magnetic field (cold forming～cryogenic forming) makes hardening of resin, afterwards, then implement heat treatment, cool off, make rare-earth adhesive magnet (sample No.16c, 17c, 18c).
Ferromagnetic powder: Sm (Co 0.672Fe 0.22Cu 0.08Zr 0.028) 8.35, average grain diameter 20 μ m
(F.S.S.S. mensuration), 97.5wt%
Binder resin: phenol resin 2.45wt%+ organic solvent, resin at room temperature are solid, soft
Change 60 ℃ of temperature.
Additive: zinc stearate 0.05wt%
Mix: use omnipotent mixer, mix on evaporation organic solvent limit, limit.
Be shaped: use hydraulic press.Forming temperature 25 ℃ of (sample No.16c), 40 ℃ of (samples
No.17c), 50 ℃ (sample No.18c).Directional magnetic field 17kOe (horizontal stroke
To magnetic field), forming pressure 30kgf/mm 2Be processed into the dumming product, at mould
In take off magnetic treatment after, from mould, take out.Formed products is shaped as a watt shape (order
Dimensioning: periphery radius of curvature R 15.00mm * interior all radius of curvature r12.00mm
* 120 ° * high 8.00mm), the radial direction directional magnetic field.
Die size: R14.70mm * r11.80mm * 120 °
Die gap heat treatment: 180 ℃ were heated 2 hours down.
For gained rare-earth adhesive magnet, the size up precision is as follows.
Formed products size: R15.01mm * r11.98mm * 120 ° * 17.46mm (n=
10 mean value), height error σ=0.58
This comparative example 5 (among the sample No.16c～18c) owing to there is not granulating working procedure, so in mould the feed instability, particularly, the finished product height easily produces error, is difficult to carry out stable formation.In order to carry out feed, must be with drift clamp-oning up and down to a certain degree, and make the curring time lengthening, and there is not the raw material of feed then to stick to the drift side, must the cleaning drift.
Embodiment 14
Following ferromagnetic powder and binder resin (thermosetting resin) are mixed, carry out this mixture mixing, again should mixing thing granulation (whole grain), obtain coccoid, this coccoid is packed under room temperature in the mould, no magnetic field lower compression be shaped (cold forming), then implement heat treatment and make hardening of resin, afterwards, cooling makes rare-earth adhesive magnet (sample No.19c).
Ferromagnetic powder: Nd 12.0Fe 77.8Co 4.3B 5.9, average grain diameter 25 μ m (survey with F.S.S.S.
98.0wt% (amount in the magnet is roughly the same) calmly),
Binder resin: bisphenol A type epoxy resin+ammonia is curing agent, amounts to 2.0wt%, resin
At room temperature be aqueous.
Mix: use omnipotent mixer to mix.
Mixing: as to use the kneading type mixing roll mixing.
Granulation: use the squash type comminutor, get the following shot-like particle of 0.6mm sieve mesh.Average grain diameter
0.4mm。
Be shaped: use hydraulic press, the forming temperature room temperature.Forming pressure 50gkf/mm 2Be processed into
The dumming product.Cylindric (target size: external diameter  10.00mm that formed products is shaped as
* internal diameter  8.00mm * high 7.00mm)
Die size: the die gap of external diameter  9.65mm * internal diameter  7.75mm
Heat treatment: 150 ℃ were heated 1 hour down.
For the rare-earth adhesive magnet that obtains, size up precision, magnetic property, density, porosity are as follows.
Formed products size: locate footpath  9.99mm * internal diameter  57.98mm * height 7.02mm (n=
10 mean value), height error σ=0.030
Magnetic property: Br=7.51kg, iHc=9.67kOe, (BH) max=11.5MGOe
Density: 6.44g/cm 3
Porosity: 5.40%
(magnetic property is measured, and after carrying out pulse and magnetic with 40kOe, applies magnetic with maximum
Field 25kOe measures with direct current magnetic-measurement machine.)
This embodiment 14, when loading (feed) in mould, amount of fill can finely be adjusted, and the result can think to obtain high dimensional accuracy.And, having excellent magnetic characteristics, porosity is low.
Comparative example 6
To mix with embodiment 14 identical ferromagnetic powder and binder resins (thermosetting resin).This mixture is mixing, and in the mould of the forming machine of again will this mixing thing packing into, no magnetic field lower compression is shaped (cold forming), then implements heat treatment and makes hardening of resin, and afterwards, cooling makes rare-earth adhesive magnet (sample No.20c).
Create conditions, except not carrying out the granulation, other is identical with embodiment 14.
For gained rare-earth adhesive magnet, the size up precision is as follows.
Formed products size: external diameter  9.99mm * internal diameter  7.98mm * high 6.72mm (n=10
Mean value), height error σ=0.86
In this comparative example 6,,, be difficult to carry out stable formation so the height of feed instability, particularly formed products easily produces error in mould owing to do not carry out granulating working procedure.For feed, must carry out to a certain degree extruding up and down with drift, the result makes the curring time lengthening.And the raw material that does not have feed then sticks on the drift side, must the cleaning drift.
Embodiment 15
Following ferromagnetic powder, binder resin (thermoplastic resin) and additive are mixed, again that this mixture is mixing, should mixing thing carry out granulation (whole grain) and obtain coccoid, again this coccoid is filled under room temperature in the mould of forming machine, no magnetic field lower compression is shaped (hot forming), and cools off, makes rare-earth adhesive magnet (sample No.21c～27c).
Ferromagnetic powder: Nd 12.0Fe 77.8Co 4.3B 5.9, average grain diameter 25 μ m (F.S.S.S. mensuration),
97.2wt% (amount in the magnet is roughly the same)
Binder resin: polyamide (PA12) resin, 1.4wt%
Additive: hydrazine is antioxidant 1.4wt%
Mix: identical with embodiment 11.
Mixing: as to use twin shaft extruding mixing roll.150～250 ℃ of melting temperatures, screw rod revolution 100
～250rpm spues with the cylindric of  10mm, makes long 5～15mm's
Particle.
Granulation: carry out the granularity adjustment by pulverizing, classification.Maximum particle diameter and average grain diameter can references
Table 26.
Be shaped: use hydraulic press.230 ℃ of forming temperatures, forming pressure 10kgf/mm 2Be shaped
Cylindric (target size: external diameter  18.00mm * internal diameter  14.00 that product are shaped as
Mm * high 10.00mm), feed is that coccoid (granulation product) is taken by weighing 6.44g,
All evenly flow in the die orifice gap along peripheral direction.
For the rare-earth adhesive magnet that obtains, measure density, porosity, formed products height, as shown in Table 26.
As shown in Table 26, along with the particle diameter of the coccoid of granulation diminishes, porosity presents increase tendency.The reason of inferring of this situation is when particle diameter is very little, to be involved in the shaping due to a large amount of air.
Therefore, the maximum particle diameter lower limit of coccoid is preferably 0.01mm, and better 0.02mm is especially good when getting 0.05mm.
The maximum particle diameter of coccoid is easy to feed in mould when the minimum dimension (2.0mm) in die orifice gap is following.Each sample, scale error are all in ± 5/100mm, so dimensional accuracy is very high.
Embodiment 16
Following ferromagnetic powder, binder resin (thermoplastic resin) and additive are mixed, again that this mixture is mixing, should carry out granulation (whole grain) by mixing thing, get coccoid, this coccoid is packed under room temperature in the mould of forming machine, and no magnetic field lower compression is shaped (hot forming), cools off, makes rare-earth adhesive magnet (sample No.28c～33c).
Ferromagnetic powder: Nd 12.0Fe 77.8Co 4.3B 5.9, average grain diameter 25 μ m (survey with F.S.S.S.
97.0wt% (amount in the magnet is roughly the same) calmly),
Binder resin: polyamide (PA12) resin+polyamide (PA6-12), PA12/
The ratio of PA6-12=5/5, total 1.6wt%
Additive: hydrazine is antioxidant 1.4wt%
Mix: identical with embodiment 11.
Mixing: identical with embodiment 15.
Granulation:, make maximum particle diameter 5mm (average grain diameter 2mm) by pulverizing and classification.
Be shaped: use hydraulic press.230 ℃ of forming temperatures, forming pressure 10kgf/mm 2Be shaped
Product are shaped as tabular (target size: banner 10.00mm * thick amm (a
Represent variable) * high 10.00mm)
In addition, during shaping, use to have die size: a plurality of moulds of the die gap of 10.00mm * amm (a is as shown in the table 27).At this moment, a size is only managed variation, but the height of formed products still is 10mm, adjusts the amount (shown in the table 27) of dress coccoid in the die orifice gap.
The weight and the elevation measurement of gained rare-earth adhesive magnet (formed products) the results are shown in the table 27.
Shown in table 27, for the minimum dimension a in die orifice gap, the maximum particle diameter of coccoid is relatively more little, and scale error is more little.Particularly, as size a (sample No.31c～33c), can obtain very high dimensional accuracy when coccoid maximum particle diameter (5mm) is above.
Embodiment 17
After compression molding, when down implementing heat treatment in 5 minutes for 230 ℃, other is the same with embodiment 15, makes rare-earth adhesive magnet (sample No.34c～40c).Measurement result and table 26 are roughly the same.
Embodiment 18
After compression molding, to implement outside the heat treatment in 3 minutes down in 200 ℃, other is the same with embodiment 16, makes rare-earth adhesive magnet (sample No.41c～46c).Measurement result and table 27 are roughly the same.
As mentioned above, according to the present invention, even with the small number of bonded resin, also can provide have excellent moldability, porosity is low, mechanical strength is high, corrosion-resistant (durability) property is good, and dimensional stability (dimensional accuracy) is high, the rare-earth adhesive magnet of excellent in magnetic characteristics.
At this moment, the particle diameter of coccoid is within the limits prescribed the time, and porosity is extremely low, and can further improve dimensional stability.
By utilizing hot forming, can lower forming pressure make the rare-earth adhesive magnet of above-mentioned characteristic, and easy to manufacture.Therefore, can reduce manufacturing expense, also be suitable for producing in enormous quantities.
Particularly, the 2nd temperature during cooling (remove and press temperature) is below the fusing point of used thermoplastic resin, and then under the temperature below the heat distortion temperature, do not depart from the set point of temperature of the 1st temperature when above, can provide porosity extremely low, the rare-earth adhesive magnet that dimensional stability is high.
Needless to say more, the raising of the raising of magnetic characteristic, the raising of corrosion resistance and dimensional stability when being applied to miniature motor, has been made very big contribution to the raising of its performance.
Table 1
Resin No. Binder resin (thermoplastic resin) Melting point [℃] Heat distortion temperature [℃]
A Polyamide (PA12) 178 145
B Polyamide (copolymer p A6-12) 145 46
C Polyamide (PA6) 215 180
D Acrylic resin (PP) 174 105
E Polyvinyl resin (PE) 128 86
F Copolyester (liquid crystal polymer-: LCP) 280 180
G Polyphenylene sulfide (PPS) 287 260
Table 2 (embodiment 1)
Sample No. Binder resin Melting temperature [℃] Forming temperature [℃] Remove to press temperature [℃] Forming pressure [kgf/mm 2]
1a A 150～250 220 100 10
2a B 100～250 200 40 15
3a A(75％) +B(25％) 150～250 230 120 10
4a A(50％) +B(50％) 140～250 210 40 7.5
5a C 190～290 250 150 20
6a D 120～250 210 90 25
7a E 100～200 150 70 10
8a F 200～350 320 140 30
9a G 260～360 300 240 25
Table 3 (embodiment 1)
Sample No. Br [kG] iHc [kOe] (BH)max [MGOe] Density [g/cm 3] Porosity [%] Mechanical strength [kgf/mm 2] Corrosivity [time]
1a 7.21 9.26 10.1 6.01 0.59 7.90 ＞500
2a 7.19 9.31 10.0 6.03 0.73 7.45 ＞500
3a 7.23 9.23 10.1 6.03 0.37 7.78 ＞500
4a 7.22 9.21 10.0 6.03 0.49 7.60 ＞500
5a 7.27 9.27 10.0 6.08 0.92 8.10 300
6a 7.24 9.35 10.3 5.88 0.58 6.95 300
7a 7.23 9.30 10.2 5.95 0.38 5.80 350
8a 7.03 9.12 9.8 6.29 0.64 9.65 450
9a 7.01 9.10 9.8 6.27 0.59 9.73 450
Table 4
Resin No. Binder resin (thermosetting resin) Softening temperature [℃] Curing condition
H Bisphenol A type epoxy resin Room temperature following (about 10 ℃) 150℃×1hr
I Phenolic resin varnish type epoxy resin 80 170℃×2hr
J Phenolic resin 70 180℃×4hr
Table 5 (embodiment 2)
Sample No. Binder resin Melting temperature [℃] Forming temperature [℃] Remove to press temperature [℃] Forming pressure [kgf/mm 2]
10a H Room temperature Room temperature 5 60
11a H Room temperature Room temperature 5 65
12a I 80～100 120 50 70
13a I 80～100 120 50 100
14a J 70～90 100 50 100
15a J 70～90 100 50 120
Table 6 (embodiment 2)
Sample No. (BH)max [MGOe] Density [g/cm 2] Porosity [%] Mechanical strength [kgf/mm 2] Corrosivity [time]
10a 8.8 5.81 5.92 3.75 2000
11a 9.1 5.85 5.27 3.86 2000
12a 9.0 5.82 5.75 3.91 2000
13a 9.3 5.86 5.11 3.98 2000
14a 9.2 5.90 6.83 4.01 2000
15a 9.4 6.02 4.93 4.11 2000
Table 7 (embodiment 3)
Sample No. Mixing roll Melting temperature [℃] Revolution [rpm] Treating capacity
16a Two extrusion mixing rolls 170～320 100～250 30kg/hr
17a The roll-type mixing roll 180～300 10～100 5kg/ criticizes, 15min/ criticizes
18a Kneader 180～300 20～100 10kg/ criticizes, 30min/ criticizes
19a KCK 170～320 20～80 20kg/hr
Table 8 (embodiment 3)
Sample No. (BH)max [MGOe] Density [g/cm 3] Porosity [%] Mechanical strength [kgf/mm 2] Corrosivity [time]
16a 15.2 6.63 0.65 8.14 ＞1000
17a 15.5 6.65 0.35 8.23 ＞1000
18a 14.9 6.61 0.95 8.09 ＞1000
19a 15.3 6.63 0.65 8.19 ＞1000
Table 9 (embodiment 4)
Sample No. The average grain diameter of shot-like particle [mm] Formed products weight [mg] Density [g/cm 3] Porosity [%] Highly [mm]
23a 2 1073 5.78 0.30 4.95
24a 1.8 1075 5.78 0.30 4.96
25a 1.5 1077 5.78 0.30 4.97
26a 1 1079 5.78 0.30 4.98
27a 0.5 1083 5.79 0.12 4.99
28a 0.1 1081 5.79 0.12 4.98
29a 0.05 1080 5.76 0.64 5.00
30a 0.01 1075 5.72 1.33 5.01
31a 0.007 1071 5.68 2.02 5.03
Notes) mean value of formed products weight and height, n=10
Table 10 (embodiment 5)
Sample No. Binding resin Forming temperature [℃] (BH)max [MGOe] Density [g/cm 2] Porosity [%] Mechanical strength [kgf/mm 2]
32a A 150 17.0 6.21 2.52 5.10
33a A 180 17.5 6.28 1.42 7.10
34a A 200 18.2 6.34 0.48 7.70
35a A 300 17.8 6.32 0.79 7.61
36a A 360 16.2 6.32 0.79 7.55
37a F 190 16.9 6.36 2.70 8.10
38a F 220 17.1 6.40 2.09 8.51
39a F 250 17.5 6.44 1.48 9.25
40a F 300 18.0 6.50 0.56 9.78
41a F 350 17.6 6.50 0.56 9.65
42a F 400 15.5 6.50 0.56 9.60
Table 11 (embodiment 6)
Sample No. Binding resin Remove to press temperature [℃] (BH)max [MGOe] Density [g/cm 3] Porosity [%] External diameter [mm]
43a A 180 8.2 6.56 2.51 10.00±0.03
44a A 170 8.5 6.62 1.62 10.01±0.03
45a A 160 8.6 6.65 1.17 10.00±0.02
46a A 140 8.6 6.67 0.87 10.01±0.02
47a A 100 8.7 6.68 0.73 10.01±0.01
48a G 283 7.7 6.60 3.53 10.03±0.04
49a G 275 7.9 6.64 2.95 10.02±0.04
50a G 260 8.3 6.74 1.49 10.01±0.03
51a G 240 8.5 6.78 0.90 10.00±0.01
52a G 200 8.5 6.79 0.76 10.00±0.01
Notes) external diameter is calculated by the measured value of n=10
Table 12 (embodiment 7)
Sample No. Forming temperature [℃] Br [kG] iHc [kOe] (BH)max [MGOe] Density [g/cm 3] Porosity [%] Mechanical strength [kgf/mm 2]
1b 170 6.87 9.91 10.2 6.14 3.74 6.97
2b 175 6.94 9.90 10.6 6.20 2.80 6.99
3b 180 7.05 9.92 11.4 6.30 1.23 7.11
4b 200 7.08 9.91 11.5 6.33 0.76 7.53
5b 220 7.07 9.90 11.5 6.33 0.76 7.51
6b 240 7.04 9.85 11.2 6.31 1.07 7.58
Table 13
Powder No. Kind Form Average grain diameter [μ m]
1 Nd-Fe-B Nd 12.0Fe 77.8Co 4.3B 5.9 22
2 Sm-Co Sm(Co 0.672Fe 0.22Cu 0.08Zr 0.028) 8.35 15
3 Nanocrystal Nd-Fe-B Nd 5.5Fe 66B 18.5Co 5Cr 5 24
4 Sm-Fe-N Sm 2Fe 17N 3 2
5 HDDR Nd-Fe-B Nd 12.6Fe 69.3Co 12.0B 6.0Zr 0.1 25
Table 14 (embodiment 8)
Sample No. Powder No. Remove to press temperature [℃] Density [g/cm 3] Porosity [%] Out of roundness [μ m]
7b 1 185 5.81 3.97 29.9
8b 1 170 5.88 2.81 17.3
9b 1 155 5.93 1.98 12.7
10b 1 140 6.00 0.82 5.2
11b 1 100 6.01 0.66 4.1
12b 2 190 6.34 4.22 29.5
13b 2 180 6.36 3.91 27.6
14b 2 170 6.42 3.00 21.0
15b 2 155 6.49 1.95 12.5
16b 2 140 6.57 0.74 5.5
17b 2 110 6.59 0.43 4.8
18b 3 180 5.82 3.80 29.1
19b 3 165 5.93 1.98 19.3
20b 3 140 5.98 1.16 7.6
Under connect table 15
Table 15 (embodiment 8)
Sample No. Powder No. Remove to press temperature [℃] Density [g/cm 3] Porosity [%] Out of roundness [μ m]
21b 3 125 6.00 0.82 5.4
22b 3 90 6.02 0.49 4.6
23b 2(75％)+4(25％) 182 6.27 3.17 29.1
24b 2(75％)+4(25％) 175 6.29 2.87 23.1
25b 2(75％)+4(25％) 160 6.35 1.98 21.3
26b 2(75％)+4(25％) 135 6.44 0.55 7.4
27b 2(75％)+4(25％) 80 6.46 0.24 3.8
28b 5 175 5.92 2.14 19.7
29b 5 150 5.94 1.81 10.1
30b 5 135 6.00 0.82 6.1
31b 5 100 6.00 0.82 4.0
Table 16
Resin No. Binder resin (thermoplastic resin) Fusing point [℃] Heat distortion temperature [℃] Melting temperature [℃] Forming temperature [℃]
A Polyamide (PA12) 178 145 150～250 230
B Polyamide (copolymer p A6-12) 145 46 100～250 200
C Polyamide (PA6) 215 180 200～280 270
D Acrylic resin (PP) 174 105 140～250 220
E Polyvinyl resin (PE) 128 86 100～200 180
F Liquid crystal polymer (LCP) 280 180 250～350 320
G Polyphenylene sulfide (PPS) 287 260 270～350 300
A+B Polyamide (mixing) (PA12: 50%+PA6-12: 50%) 162 (scaled values) 96 (scaled values) 120～250 200
Table 17 (embodiment 9)
Sample No. Resin No. Remove to press temperature [℃] Density [g/cm 3] Porosity [%] Out of roundness [μ m]
32b A 185 6.57 4.03 29.6
33b A 170 6.65 2.86 22.1
34b A 140 6.79 0.81 17.8
35b A 110 6.81 0.52 7.7
36b A(50％)+B(50％) 175 6.65 3.07 38.4
37b A(50％)+B(50％) 150 6.72 2.05 32.1
38b A(50％)+B(50％) 135 6.74 1.76 26.7
39b A(50％)+B(50％) 60 6.79 1.03 7.1
40b A(50％)+B(50％) 40 6.82 0.59 3.6
Under connect table 18
Table 18 (embodiment 9)
Sample No. Resin No. Remove to press temperature [℃] Density [g/cm 3] Porosity [%] Out of roundness [μ m]
41b C 215 6.68 4.00 26.6
42b C 210 6.70 3.72 21.1
43b C 190 6.74 3.14 15.5
44b C 170 6.80 2.28 9.6
45b C 125 6.92 0.56 6.4
46b D 180 6.47 3.54 28.9
47b D 165 6.52 2.80 20.9
48b D 115 6.57 2.05 16.6
49b D 95 6.68 0.41 7.8
50b E 125 6.53 3.53 19.6
51b E 110 6.57 2.93 15.3
Under connect table 19
Table 19 (embodiment 9)
Sample No. Resin No. Remove to press temperature [℃] Density [g/cm 3] Porosity [%] Out of roundness [μ m]
52b E 95 6.63 2.05 12.1
53b E 78 6.70 1.01 9.6
54b F 290 6.90 3.43 36.6
55b F 275 6.95 2.73 18.6
56b F 250 6.98 2.31 15.3
57b F 190 7.08 0.91 7.1
58b F 170 7.11 0.49 3.6
59b G 292 6.86 3.66 30.0
60b G 280 7.05 0.99 7.2
61b G 255 7.09 0.43 3.8
62b G 200 7.09 0.43 3.4
Table 20
Form Ferromagnetic powder [wt%] Binder resin [wt%] Antioxidant [wt%] Other additive [wt%]
Form 1 92.0 7.1 0.7 Silicone oil 0.2
Form 2 94.0 4.7 1.2 Oleic acid 0.1
Form 3 96.0 2.4 1.6 -
Form 4 98.0 1.0 1.0 -
Table 21 (embodiment 10)
Sample No. Form Remove to press temperature [℃] Density [g/cm 3] Porosity [%] Out of roundness [μ m] (BH)max [MGOe]
63b Form 1 178 4.81 3.97 29.4 6.0
64b Form 1 170 4.83 3.58 27.1 6.1
65b Form 1 140 4.86 2.98 22.1 6.1
66b Form 1 100 4.99 0.38 4.1 6.2
67b Form 2 178 5.27 3.79 27.9 7.0
68b Form 2 170 5.30 3.24 24.5 7.0
69b Form 2 140 5.35 2.33 17.1 7.1
70b Form 2 100 5.45 0.50 4.4 7.1
Under connect table 22
Table 22 (embodiment 10)
Sample No. Form Remove to press temperature [℃] Density [g/cm 3] Porosity [%] Out of roundness [μ m] (BH)max [MGOe]
71b Form 3 180 5.82 3.91 28.9 9.2
72b Form 3 178 5.87 3.09 23.8 9.4
73b Form 3 170 5.89 2.76 17.8 9.6
74b Form 3 140 6.01 0.78 5.5 10.0
75b Form 3 100 6.02 0.61 4.3 10.1
76b Form 4 185 6.52 3.10 27.6 10.5
77b Form 4 178 6.57 2.36 19.7 10.6
78b Form 4 170 6.59 2.02 14.0 10.9
79b Form 4 140 6.62 1.62 5.1 11.2
80b Form 100 6.66 1.02 4.8 11.4
Table 23
Ferromagnetic powder Resin Additive
Form 1 Nd-Fe-B (94.0wt％) Polyamide (No.A in the table 1) (4.8wt%) Hydrazine class antioxidant (1.2wt%)
Form 2 Nd-Fe-B (97.0wt％) Polyamide (No.A in the table 1) (1.5wt%) Hydrazine class antioxidant (1.5wt%)
Form 3 Sm-Co (92.5wt％) PPS resin (No.G in the table 1) (7.45wt%) Stearic acid (0.05wt%)
Form 4 Sm-Co+Sm-Fe-N (71+24wt％) Acrylic resin (No.D in the table 1) (4.9wt%) Silicone oil (0.1wt%)
Form 5 Nanocrystal Nd-Fe-B (96.0wt%) Polyamide (PA11: 150 ℃ of heat distortion temperatures) (3.0wt%) Hydrazine is antioxidant (1.0wt%)
Form 6 Nd-Fe-B (HDDR method) (95.5wt%) Liquid crystal polymer (No.F in the table 1) (3.3wt%) Phenol is antioxidant (1.2wt%)
Nd-Fe-B: Nd 12.0Fe 77.8Co 4.3B 5.9Average grain diameter 15 μ m
Sm-Co: Sm (Co 0.672Fe 0.22Cu 0.08Zr 0.028) 8.35Average grain diameter 18 μ m
Sm-Fe-N: Sm 2Fe 17N 3Average grain diameter 2 μ m
Nanocrystal Nd-Fe-B:Nd 5.5Fe 66B 18.5Co 5Cr 5Average grain diameter 20 μ m
Nd-Fe-B (HDDR method): Nd 12.6Fe 69.3Co 12.0B 6.0Zr 0.1Average grain diameter 20 μ m
Table 24 (embodiment 11)
Sample No. Raw material Forming temperature [℃] Br [kG] iHc [kOe] (BH)max [MGOe] Density [g/cm 3] Porosity [%]
1c Form 1 210 5.88 9.09 6.9 5.44 0.79
2c Form 2 230 7.48 9.32 11.2 6.33 0.81
3c Form 3 300 6.48 9.18 9.2 5.98 1.81
4c Form 4 200 9.05 12.02 17.5 6.54 0.94
5c Form 5 220 7.43 4.47 7.7 5.81 0.95
6c Form 6 290 8.55 13.7 15.9 6.12 1.10
Sample No.1c, 2c, 5c, no magnetic forming
Sample No.3c, 4c, 6c, magnetic forming (applying radial magnetic field 15kOe)
Table 25 (comparative example 3)
Sample No. Raw material Forming temperature [℃] Forming pressure [kgf/mm 2] Remove to press temperature [℃] Density [g/cm 3] Porosity [%]
7c Form 1 100 80 50 4.98 9.18
8c Form 2 120 80 50 5.70 10.68
9c Form 3 235 80 100 5.52 9.37
10c Form 4 90 80 30 5.35 8.79
11c Form 5 80 80 50 5.41 10.42
12c Form 6 150 80 60 5.44 12.10
Sample No.7c, 8c, 11c, no magnetic forming
Sample No.9c, 10c, 12c, magnetic forming (applying radial magnetic field 15kOe)
Table 26 (embodiment 15)
Sample No. The granular maximum particle diameter [mm] of stopping Coccoid average grain diameter [mm] Formed products density [g/cm 3] Porosity [%] Formed products height [mm]
21c 2.0 1.5 6.42 0.42 9.95
22c 1.0 0.8 6.42 0.42 9.99
23c 0.5 0.45 6.41 0.58 10.00
24c 0.3 0.2 6.40 0.73 10.00
25c 0.1 0.05 6.37 1.20 10.02
26c 0.05 0.04 6.30 2.28 10.04
27c 0.02 0.01 6.26 2.50 10.05
Table 27 (embodiment 16)
Sample No. A size [mm] Coccoid loading [g] Formed products weight [g] Formed products length [mm]
28c 4.0 2.53 2.31 9.12
29c 4.5 2.85 2.66 9.35
30c 4.8 3.04 3.01 9.90
31c 5.0 3.17 3.15 9.95
32c 5.5 3.48 3.48 10.00
33c 6.0 3.8 3.79 9.99
Owing to have above-mentioned effect, rare-earth adhesive magnet of the present invention, for example can be applicable to constitute various motor such as stepping motor, unit's brush motor and solenoid, transmission device etc. permanent magnet, be configured for the transducer etc. of automobile etc. permanent magnet, constitute the permanent magnet of detector such as VTR, as various permanent magnet such as meter classes.

Claims (23)

1. the manufacture method of a rare-earth adhesive magnet, feature be, the rare earth element magnet powder is carried out the manufacture method of bonding rare-earth adhesive magnet by binder resin, comprises following operation, promptly;
With above-mentioned rare earth element magnet powder and above-mentioned binder resin mix, mixing, make the operation of mixing thing,
Above-mentioned mixing thing is carried out granulation or whole operation of making coccoid,
Use above-mentioned coccoid, under the 1st temperature of or molten condition softening, carry out the operation of press molding at described binder resin,
At least under pressurized state, be cooled to be lower than under the 2nd temperature of described the 1st temperature the operation of cooling off.
2. according to the manufacture method of the rare-earth adhesive magnet of claim 1 record, feature is that above-mentioned binder resin is a thermoplastic resin.
3. according to the manufacture method of rare-earth adhesive magnet of record in claim 1 or 2, feature is above-mentioned mixing, under the temperature more than the heat distortion temperature of above-mentioned binder resin and become by fusion or softening binder resin composition above-mentioned rare earth element magnet powder surface to be formed under the state that coats and carry out.
4. according to the manufacture method of the rare-earth adhesive magnet of record in claim 1 or 2, feature is that the rare earth element magnet content of powder in the above-mentioned mixing thing is 90～99wt%.
5. according to the manufacture method of the rare-earth adhesive magnet of record in claim 1 or 2, feature is to contain antioxidant in the above-mentioned mixing thing.
6. according to the manufacture method of the rare-earth adhesive magnet of record in claim 1 or 2, feature is that the average grain diameter of above-mentioned coccoid is 0.01～2mm.
7. according to the manufacture method of the rare-earth adhesive magnet of record in claim 1 or 2, feature is fusing point or the heat distortion temperature that above-mentioned the 2nd temperature is above-mentioned binder resin.
8. according to the manufacture method of rare-earth adhesive magnet of record in claim 1 or 2, pressure when feature is cooling under above-mentioned pressurized state keeps constant at least under the temperature during the 1st temperature arrives the 2nd temperature.
9. the manufacture method of a rare-earth adhesive magnet, feature is to be undertaken the rare earth element magnet powder bonding by the binder resin that is formed by thermoplastic resin, form the manufacture method of rare-earth adhesive magnet, comprise: the composition that will contain above-mentioned rare earth element magnet powder and above-mentioned binder resin, soften or form under the 1st temperature of molten condition at described binder resin, carry out the operation of press molding and under pressurized state, be cooled to be lower than the operation of the 2nd temperature of above-mentioned the 1st temperature at least.
10. the manufacture method of a rare-earth adhesive magnet, feature is by the binder resin that is formed by thermoplastic resin the rare earth element magnet powder to be carried out the bonding manufacture method that forms rare-earth adhesive magnet, comprises following operation, promptly
The composition that will contain above-mentioned rare earth element magnet powder and above-mentioned binder resin under the temperature more than the heat distortion temperature of above-mentioned binder resin, carries out mixing operation,
Under the 1st temperature of above-mentioned mixing composition is softening at above-mentioned binder resin or molten condition, carry out press molding operation and
Under pressurized state, be cooled to the operation of the 2nd following temperature of above-mentioned the 1st temperature at least.
11. according to the manufacture method of the rare-earth adhesive magnet of record in claim 9 or 10, feature is fusing point or the heat distortion temperature that above-mentioned the 2nd temperature is above-mentioned binder resin.
12. according to the manufacture method of rare-earth adhesive magnet of record in claim 9 or 10, feature is that the difference of above-mentioned the 1st temperature and the 2nd temperature is more than 20 ℃.
13. according to the manufacture method of rare-earth adhesive magnet of record in claim 9 or 10, feature is the cooling under the above-mentioned pressurized state, is the pressure when not removing above-mentioned press molding, and carries out continuously.
14. according to the manufacture method of rare-earth adhesive magnet of record in claim 9 or 10, feature is the forming pressure during with respect to press molding, the pressure during cooling above-mentioned pressurized state under is equal or be lower than this pressure.
15. according to the manufacture method of rare-earth adhesive magnet of record in claim 9 or 10, feature is the pressure during cooling above-mentioned pressurized state under, during the fusing point of the above-mentioned binder resin of arrival, keeps constant at least always.
16. according to the manufacture method of rare-earth adhesive magnet of record in claim 9 or 10, feature is that the cooling rate when cooling off above-mentioned pressurized state under is 0.5～100 ℃/second.
17. according to the manufacture method of rare-earth adhesive magnet of record in claim 9 or 10, the forming pressure when feature is above-mentioned press molding is at 60kgf/mm 2Below.
18. rare-earth adhesive magnet, feature is, the rare-earth adhesive magnet that utilizes hot forming to make, thermoplastic resin softening or molten condition in the time of will being shaped under pressurized state is cooled to be lower than the temperature of forming temperature, with the rare earth element magnet powder-stuck, and porosity is below 4.5vol% by the above-mentioned thermoplastic resin that solidifies.
19. rare-earth adhesive magnet, feature is the rare-earth adhesive magnet that utilizes hot forming to make, under pressurized state, the thermoplastic resin of softening or molten condition when being shaped, be cooled to the temperature that its heat distortion temperature is following or fusing point is following, by the above-mentioned thermoplastic resin that solidifies together, and porosity is below 4.0vol% with the rare earth element magnet powder-stuck.
20. rare-earth adhesive magnet, the coccoid that feature is to use granulating working procedure to make, rare-earth adhesive magnet by the hot forming manufacturing, under pressurized state, the thermoplastic resin of softening or molten condition is cooled to the temperature that its heat distortion temperature is following or fusing point is following when being shaped, by the described thermoplastic resin that solidifies with the rare earth element magnet powder-stuck together, and porosity is below 4.0vol%.
21. according to the rare-earth adhesive magnet of each record in the claim 18～20, feature is in the magnet, above-mentioned rare earth element magnet content of powder is 92.0～99.0wt%.
22. according to the rare-earth adhesive magnet of each record in the claim 18～20, feature is that maximum magnetic flux energy product (BH) max that is shaped in no magnetic field is more than 6MGOe.
23. according to the rare-earth adhesive magnet of each record in the claim 18～20, feature is that maximum magnetic flux energy product (BH) max that is shaped in magnetic field is more than 12MGOe.
CNB971905533A 1996-03-18 1997-03-18 Process for producing rare earth bond magnet, composition for rare earth bond magnet, and rare earth bond magnet Expired - Fee Related CN1143332C (en)

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JP61495/96 1996-03-18
JP8061495A JPH09260170A (en) 1996-03-18 1996-03-18 Manufacture of rare earth bond magnet and composition for rare earth bond magnet
JP61495/1996 1996-03-18
JP77642/1996 1996-03-29
JP07764296A JP3653852B2 (en) 1996-03-29 1996-03-29 Rare earth bonded magnet manufacturing method and rare earth bonded magnet
JP77642/96 1996-03-29
JP161274/1996 1996-06-21
JP161274/96 1996-06-21
JP16127496A JP3658868B2 (en) 1996-06-21 1996-06-21 Rare earth bonded magnet manufacturing method and rare earth bonded magnet

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